CN1468279A - Flexible polymer element as toughening agent in prepregs - Google Patents

Abstract

A flexible polymer element for a curable composition wherein the flexible polymer element is in solid phase and adapted to undergo at least partial phase transition to fluid phase on contact with a component of the curable composition in which it is soluble at a temperature which is less than the temperature for substantial onset of gelling and/or curing of the curable composition; a method for the preparation thereof, a support structure or carrier for a curable composition comprising the at least one flexible polymer element together with reinforcing fibres, configurations of support structures and carriers, methods for preparation thereof, a curable composition comprising the at least one flexible polymer element or the support structure or carrier and a curable resin matrix, a kit of parts comprising the components thereof and a method for selection thereof, a method for preparation and curing thereof, and a cured composite or resin body obtained thereby, and known and novel uses thereof.

Description

In prepreg, be used as the flexible polymer element of toughner

Technical field

The present invention relates to a kind of flexible polymer element that is used for curable compositions and preparation method thereof, wherein said parts are suitable for being dissolved in the curable compositions; The invention still further relates to the supporting structure that a kind of curable compositions uses is that carrier, supporting structure are structure of carrier and preparation method thereof, described supporting structure is that carrier comprises at least one flexible polymer element and fortifying fibre, and described curable compositions comprises at least one flexible polymer element or supporting structure is carrier and curable resin matrix; The present invention has also disclosed cover parts, and system of selection, preparation method and curing, thus obtained cured composite or resinite and their known and new purposes.

The present invention relates to a kind of flexible polymer element that is forms such as fiber, film and preparation method thereof or rather, and the supporting structure that is the curable compositions of forms such as fabric is carrier and related fields content thereof.

Technical background

Fibre-reinforced resin base material mixture is widely used as the engineering materials of high strength light weight, replaces metal in purposes such as aircraft structure.These matrix materials can be made by laminating prepreg, and described prepreg comprises high strength fibre, for example glass fibre, graphite (carbon) fiber, boron fibre etc., and these fibers are with general thermoplastic resin base material dipping.The key property of these mixtures is high strength and high rigidity and light weight.

Except the common requirement that can bear all possible load and stress types, not stratified, anti-fracture etc., mixture must satisfy the very harsh requirement of aforementioned properties, aforementioned properties stand envrionment conditions comprise extreme temperature (heat-resisting cycle performance), be exposed to UV-light and other types radiation, be exposed to atmosphericoxygen (resistance to oxidation), be exposed to moisture etc., standing to endanger under the situations such as for example being exposed to solvent, influence contains the security of the structure of described mixture greatly.

Contain the feature of curable compositions of fluoropolymer resin and the blend that may also contain fortifying fibre,, so just can select composition by concrete purposes in polymer resin components and the fibre fractionation physicals and the chemical property separately of its formation.Therefore, generally have thermoset resin components to exist, it produces high solvent resistance and heat-resisting cycle performance etc.Except the thermoplastic resin component who produces high tenacity etc. is arranged, produce high inflexible fortifying fibre in addition, be used for weight reduction.

Various resins and fiber generally carry out blend or are shaped and solidify with suitable manner, and in desired finished product by physics with some situation under the interaction of chemistry keep their distribution or shape.Yet, blend or be formed under many situations can be because following factor be complicated, for example high viscosity of resin (especially when needing the dipping fortifying fibre), weak point " pot life " (pre-gelled time), the homogeneity that obtains or the dispersion state of selection etc.

Recently the other technologies of composite component occur making, be commonly referred to liquid molding (LM).This method is with the different of manufacture method of conventional prepreg, and fiber (doing) is placed in the molds/tools, matrix resin is directly injected/immerse in the fiber again.

Liquid molding (LM) is big class methods, and it comprises following all treatment technologies: resin transfer molding (RTM), liquid resin inject (LRI), resin injects soft processing (RIFT), vacuum assisted resin transfer molding (VARTM), resin molding injection (RFI) etc.Compare with the method for making of conventional prepreg, the potential advantage that LM provides is (drape) influence that reduces waste material, the shortening residence time, do not adhered and dangle, and the performance of improving lay up period.In practice, the maximum purposes of finding the LM technology is in special operation, and the composite structure body (polycomponent) of this manipulation require complexity need be distributed in carbon fiber in the mould and the local structure that strengthens selectively, with the needs very occasion of macrostructure body, the purposes of for example transporting by sea.

Resin molding injects (RFI) LM technology and conventional prepreg method for making is combined, for example in RTM or the curing of RFI thermal compressor, prepreg orientation in accordance with regulations is stacked into sandwich one by one, this sandwich is placed against slick metal sheet, and the successive layers with porous Teflon, emission performance fabric and vacuum bag covers then.Applying compaction pressure to this sandwich makes its compacting and squeezes out the volatile matter bubble that stays.Use thermal compressor can limit the size of the parts that can be made into.For example, can not use thermal compressor to build hull, yacht or bridge at present,, just increase equipment cost and running cost because this needs the thermal compressor of huge supercharging.

VARTM uses the mould that one side is only arranged and adopts vacuum bagged technique compresses preform, has just simplified die RTM.But if resin can not solidify before filling up mould really, the time of filling mould can be oversize.

The filling time of RIFT is with regard to much shorter.The porous layer that flow resistance is very low " distribution medium " provides the easily approach of circulation for injecting resin.Resin can flow through the distribution medium that is placed on above the sandwich fast, is downward through the whole thickness of prefabrication then.Use fiber form passage that resin injects be known (WO0102146A1) (Plastech), US5484642 (Brochier), US5326462 (Seemann).But these passages can be mobile in the degassing and solidification process, and if they stay, they just are kept perfectly after curing.

The problem that the end user can run into is to be difficult at present prepare qualified parts from thermal compressor with RIFT or VARTM.Only be cured, can make parts have very high void content, make bad mechanical property with vacuum solidification or without pressure.

Our accident has been found a kind of method now, can obtain composition board again at barometric point or only be to be cured under the condition of vacuum with VARTM and RIFT, and this method is easy to injection, and the goods void content is near 0%.The present invention also uses fiber in degasification process, this fiber is not present in the final hardening element.

A common shortcoming of prepreg and LM technology is present in the very tough field of compound material.Resin impregnation or for example person's character requirement of carbon fibre fabric method of injection fortifying fibre.Its rheological, viscosity and elasticity can allow resin penetration pass through fabric.If made composite structure body does not have the space, and if avoid long dipping time or inject time and high injection temperature, above-mentioned requirements is exactly essential so.

Resin system with high impact resistance contains thermoplastic toughening agent etc. usually, and they can increase the viscosity and the elasticity of resin, makes them be difficult to dipping or injection.This just needs high dipping and injection temperature and pressure.

A kind of method that can effectively make the thermoplastic toughening mixture is to remove thermoplastic material from resinous substrates, and is applied directly on fiber or the fabric in some way it or inside.This can adopt several method to reach.

If during with the LM technology, the shape of mixture is before injection thermoplastic material and resinous substrates, the tackiness agent that applies powder, liquid or form membrane to prefabrication fixes the shape of prefabrication and forms, just being difficult in has a large amount of thermoplastic materials and matrix in the prefabrication, and needs too high temperature and pressure.In addition, composite materials only has medium toughness, this be since can physics the amount of thermoplastic material of injection limited, and if tackiness agent and the inconsistent words of matrix, also can be subjected to the tackiness agent adverse influence.

For example also known EP392939 discloses by or comingling woven with thermoplastic fibre and fusing dipping and has prepared the prepreg that contains fortifying fibre.But these systems do not attempt adding other matrix in prepreg, and generally adopt very high-molecular weight thermoplastic polymer, melt with regard to needing very high temperature and pressure.

Someone advises using the blended thermoset resin substrate, it comprises the high-molecular-weight thermoplastic polymkeric substance, for example as described in the GB-A-2060490, disperses thing as particulate state, or as the particulate coating of fiber reinforced resin based matter prepreg or the intertexture of film, as described in US-A-5057353.But, owing to generally be difficult to control the size distribution and the particle size uniformity that can influence burn-off rate and melting degree, and owing to be present in the inhibition of intramatrical continuous film, so divide breaking up very poor.US5288547 has disclosed the prepreg that a kind of curable compositions is used, and it comprises the intertexture of porous thermoplastic polymer film.This film in conjunction with entering prepreg, specifically is that this film is placed against the fortifying fibre sheet in preparation process, and molten under high temperature and pressure membranization is come impregnation of fibers.Prepreg also can be staggeredly placed with film, with film fusing and be used for dipping, solidifies then, forms composite component.Somebody suggestion is used for the RTM technology with this film, puts between the dried layer of fibers of mould, and dipping is melted in fusing, then in the liquid resin injection mould.

The content of invention

Though above-mentioned way has relaxed desired extreme condition to a certain extent, still demand can be improved blend, greater flexibility and bigger the performance of dispersion liquid and the general way of consumption controlled of component.Specifically, thermoplastic material and resinous substrates have been got rid of the possibility of pre-blend, blend diffusion effectively when solidifying.In addition, also need in system, to add the more high-viscosity polymer of volume, for example toughner such as thermoplastic material.

We are surprised to find that we can provide composite structure intravital general high-viscosity polymer, so that overcome the problems referred to above, its form is solid-state soluble flexible polymer element.This is very unexpected, is to repel mutually because be contemplated that solubility property under the lesser temps and cohesive performance (as interior poly-parts), promptly needs low and high MW respectively, otherwise will not too effectively compromise.

In addition, we have also found a kind of method, providing the supporting structure of curable compositions without mould by flexible polymer element is carrier, described loading contains the flexible polymer element that fiber is fixed to the form that requires therein, and the latter is dissolved before solidifying or when solidifying beginning and is dispersed in the curable compositions.

The synthon that preparation is used for textile industry are viscose fiber, nylon, flame-retardant polymer etc. for example, and they are woven into the fabric with good drape and fibre strength, and this is known very early.Though some this fibrid susceptible of proof in fact dissolves in the resinous substrates of the present invention, this behavior is not observed as yet.So far, be unaware of this deliquescent benefit, with above-mentioned supporting structure be the fiber that exists of carrier format then then be used in fabric or the other industry, for example in mixture or the tackiness agent industry.

Strengthen in the technology of mixture at some, known form with firm suture is introduced thermoplastic polymer such as polyester, compound is strengthened structure to be fixed together, this structure for example is three-dimensional non-crimps (NCF), like this, fiber is fixed on the throne with just becoming row and orientation when injecting, flooding or applying thermosetting resin.The material of suture form is a high-melting-point very, 230 ℃ polymkeric substance for example, and in addition, it still is orientated, so degree of crystallinity is very high, makes can not melt or dissolve, and solidifying afterwards, suture just can be kept perfectly.

This also can produce many problems, and for example suture is to the susceptibility of moisture content, and thermal expansivity does not match, shrink, the loss of mechanical property and environmental performance, suture are usually incompatible with cured thermosetting, and owing to the uneven surface of finished product or patterned surface produce problem on attractive in appearance.

So just need a kind of improved polymkeric substance suture, fiber and textile structure is fixing on the throne, for ease of injection or dipping and curing, also should not harm the mechanical property of cured composite.

We are surprised to find that now, and flexible polymer element can provide with the form of fiber etc., and it can be used as suture, does not dissolve in curable compositions.

We also are surprised to find that, by the sticky polymers of liquid and two kinds of forms of solid-state flexible polymer element is provided, just can provide the composition of the sticky polymers component that comprises the amount of increasing.

Therefore, of the present invention the widest aspect, for curable compositions provides a kind of flexible polymer element, this flexible polymer element is a solid phase, than obvious gelling and/or the lower temperature of solidified temperature of beginning of curable compositions, the contact of this flexible polymer element it when dissolving in the component of curable compositions wherein, partial phase change becomes liquid state at least.

Flexible polymer element as herein described is the parts of Any shape, it is suitable for being partly dissolved at least in the resinous substrates that constitutes curable compositions with chemistry and physics dual mode, this polymkeric substance is just because of dissolving to small part is dispersed in the matrix as total phase thus, and this flexible polymer element has just lost its tangible element form to small part thus.

Suitable is that at least one flexible polymer element is microscler along at least one direction, for example is form such as single or plurality of fibers or long filament, band, film or their mixture or the fabric of weaving material.

Flexible polymer element is suitable in the solidified primary stage, is being warming up to the dissolving of beginning gelling and/or solidified temperature stage, curable compositions just is fixed into desired structure by flexible polymer element thus, viscosity until curable compositions increases, and just no longer needs the support of flexible polymer element or mould.

Flexible polymer element can be suitable in the processing of curable compositions, at this moment, can not have what noticeable relation by its dissolved polymers basically at the aspect of performance of curing composition.Especially advantageously can provide such flexible polymer element, it can be dissolved in the cured article, and can not show vestige in these goods, but can make it enough firm again, can be used for supporting, other components of carrying or bonding composition.In addition, flexible polymer element also can be as the component of curable compositions, and the performance of end article is worked.Also have an advantage to be, such curable compositions can also be provided, wherein can comprise sticky polymers, constitute the major portion of the polymer phase of end article.In addition, flexible polymer element can also be used to process and has the curable compositions that improves composite properties, and in final cured article no vestige or otherwise be present in the final cured article.

Of the present invention one especially favourable aspect, good dispersion is taken place in the liquid phase of flexible polymer element by the solvation of curable components.This performance for cured article is even more important.We are surprised to find that, scan raman spectrum that whole cured article obtains along coordinate and demonstrate 100% and disperse, and all carry out same scanning on each coordinate.

At a further advantageous aspect of the present invention, flexible polymer element is in room temperature or up to 300 ℃ or under 400 ℃ the high temperature, do not having under the situation of dissolving resin, favorable durability can be provided and keep solid-state, and can be in this temperature or this seasoning year in year out below temperature and form constant, then by contacting with dissolving resin and for example surpassing 60 ℃ of temperature under the defined terms in the above, desired phase transformation just can take place in for example about 140 ℃ of curing.

Phase transformation by dissolving, is aided with sometimes and adds heat and produce in the resinous substrates component of curable compositions.Especially advantageously the soluble polymer parts can improve blend.

When curable compositions solidified, the polymkeric substance of flexible member may can be suitable for forming total phase with dissolution mechanism in thermosetting resin, or can all or part ofly be separated, and forms two-phase resinous substrates system.For example EP311349 just describe thermoset/thermoplastic blend in detail toughness except outside the Pass having with other factors, relevant with form and phase size in solidifying blend.The degree of flexibility of desired matrix resin can by control in thermoset/thermoplastic blend form and phase size by chemical constitution and any other parameters acquisitions that require form of thermoplastic polymer and thermosetting resin precursor.

Figure B1 and B4 show fiber as dissolving under the flexible polymer element situation and phase separation, it is characterized in that whole dissolvings.Figure B4 has shown the two general phase morphologies that obtain in thermoplasticity/thermoset system, it can obtain from the present invention.The phase transformation of flexible member may dissolving and so on, for example TEM, SEM etc. measure or control can to adopt any suitable technique, and these technology can be used for measuring the feature of suitable flexible member may feature and curable compositions and the commercial production condition of curing composition by those of ordinary skill in the industry.

The polymkeric substance that forms flexible polymer element preferably is suitable for undergoing phase transition, and promptly the temperature T s in a temperature range is partially dissolved in the resinous substrates at least, and at least a portion scope in the described temperature range is lower than the solidification value of resinous substrates Tc.This polymer elements can be configured to improve or reduce thermal conductivity and promote or slow down the heat that passes on the parts, dissolves to accelerate or to delay.

By guaranteeing that Procuring time and temperature are not enough to whole dissolvings, perhaps preferably by provide blend or with the polymkeric substance of the multipolymer form of one or more insoluble polymers, for example random or segmented copolymer form or other blend or have the derivative of organic or inorganic matrix, all or part of phase transformation just can take place in polymer elements, for example can dissolve fully, maybe can be partly dissolved, its part just is scattered in the matrix thus, and a part keeps with the parts form.By this mode, polymer elements just can with other the solvable or insoluble organic or inorganic substrate compositions in one or more other polymkeric substance or the curing composition.

Flexible member may can contain for example conventional toughner, as has a fluid rubber of reactive group, granule is granulated glass sphere for example, rubber grain and the granulated glass sphere that is coated with rubber, metallic particles is Ti for example, Al or Fe, filler is tetrafluoroethylene for example, silicon-dioxide, graphite, boron nitride, clay is mica for example, talcum, vermiculite, pigment, nucleator and stablizer be phosphoric acid salt for example, the reagent of enhancing solvent resistance is fluorine-containing reagent for example, fire retardant is metal oxide FeO and TiO for example, with blend or the random copolymers crystalline polymer that adds of polyetherketone form for example, the for example low MW thermosetting monomer of conventional binding agent is epoxy for example, acrylic acid derivative, cyanate, ester, BMI-type polymer etc., conventional tackiness agent is epoxy polymer etc. for example, conventional coating agent etc.

According to the thickness or the diameter of flexible polymer element, particle, pearl etc. is preferably dimensioned to be nanometer and micrometer range, and clay particle is 0.5-5nm preferably, 0.1nm for example, and the Ti particle can be the 1-6 micron, for example 2 microns.

The present invention especially advantageously, such conventional flame retardants for example several percentage ratios high MW rubber for example Nippol etc. just can make conventional blend have high viscosity, flexible polymer element of the present invention is as good carrier, and the problems such as melt temperature of viscosity, incompatible polymer just can overcome thus.

Under the homodisperse situation of the polymkeric substance that requires flexible polymer element, flexible polymer element preferably is and is suitable for and the meticulous blended form of other components of curable compositions, for example with the form of fiber, long filament, belt etc., and requiring under the local dispersive situation, flexible polymer element can be any non-above-mentioned any form or other forms of being presented in subtly in other components (one or more) that be suitable for, the form of film for example is so that coating, adhere to or produce for example toughening effect of partial result.

Flexible member may preferably diameter is fiber or the long filament of d, or thickness is film or the band of t, and d or t are positioned at the scope up to 100 microns, preferred 1-80 micron, for example 30-80 micron, more preferably 30-65 micron.Flexibility is the compromise between component thickness or diameter and the polymkeric substance modulus.

Can provide to have a dawn that requires and count the fiber of Tex (fibre weight g/m, expression linear density), can in the scope of 5-150Tex, in the fiber production process, can control in known manner.

The characteristic optimization of flexible member may is that elongation at break is in the 1-75% scope, preferred 3-50%, lower than suture line purposes, than weaving the purposes height, this performance is determined by polymer type and preparation method, for example by sewing up and the orientation decision, also by toughness that Dtex weighed, based on for example fibre weight decision on the unit length of the linear density of parts.

Suitable flexible polymer element can applying, deformable, can dangle and maybe can handle, and can be present in the curable compositions of top defined with suitable manner.Be not limited to this theory, can think in the preparation process of polymer elements, can produce physics interacts, this meeting causes owing to orientation, the interaction of chain, the characteristic of single polymer chain etc. or strengthens flexible, reach especially favourable effect, elasticity, microscler performance and intensity there are contribution, can guarantee to twist together, sew up, hold etc.

Flexible polymer element can be characterized by its combination or adhesion property, described performance is given by the softening institute of for example above temperature of room temperature, or be characterized by and comprise monomer for example thermoset (epoxy) monomer or other known binding agents, help the physical bond in the foregoing curable composition.Flexible polymer element of the present invention so just is particularly useful for above-mentioned LM technology.

In principle, in curable for example thermoset resin substrate, at least can be partly soluble in its temperature below solidification value, and can form any polymkeric substance of above-mentioned flexible member may by methods such as known or for example extruding of novel method, spinning, cast, may be used in the operation of the present invention.Flexible polymer element preferably contains at second-order transition temperature or softening temperature or the temperature rubber-like polymkeric substance more than it, it be selected from natural or synthetic rubber and elastomerics, thermoplastic material and mixture, they can miscible or immiscible blend, or with other amorphous or crystalline polymkeric substance and/or monomeric random copolymers or segmented copolymer.Flexible member may more preferably contains at second-order transition temperature or the temperature below softening temperature rubber-like amorphous polymer also, more preferably contains thermoplastic polymer.Useful thermoplastic material comprises following polymkeric substance, for example derivatived cellulose, polyester, polymeric amide, polyimide, polycarbonate, urethane, polyacrylonitrile, poly-(methyl methacrylate), polystyrene, and aromatic polymer, for example polyaryl ether, poly-aryl ketones, especially polyaryl sulfone.Also can use multipolymer, for example polyesteramide, polyamidoimide, polyetherimide, aromatic poly, poly-arylide, poly-(ester) carbonic ether, poly-(methyl methacrylate/butyl acrylate), polyethersulfone-ether ketone.Also can use the blend of polymkeric substance.

Urethane comprises thermoplastic polyurethane rubber.Polymeric amide comprises that nylon and other can form the orientation long chain polymer of long filament or film, polyester comprises terephthalic acid and ethyl-1, the straight chain condenses (polyester) of 2-glycol, polyacrylic ester comprises by many monomer synthetic acrylic acid derivative fibers, described monomer comprises at least 85 weight % vinyl cyanide, derivatived cellulose comprises cellulose diacetate, viscose fiber, and polyetherketone is based on the polyetherketone of dihydroxyphenyl propane.

Thermoplastic material is aromatic polymer preferably.The polymkeric substance that aromatic polymer is preferably such, it comprises the identical or different repeating unit in the following formula:

-X-Ar-A-Ar-X-

Wherein A is selected from SO ₂, directly key, oxygen, sulphur ,-CO-or bivalent hydrocarbon radical; X is a divalent group, and as A definition, they can be identical or different, or divalence aromatic group diphenylene for example; Ar is the divalence aromatic group, or comprises any one of aromatic nucleus or the multivalence group of a plurality of substituent R, and each independently is selected from hydrogen, C each R _1-8Saturated or unsaturated fatty acids group of straight or branched or the optional for example heteroatomic part of Cl or F of one or more O of being selected from, S, N or halogen atom that contains; With the group that active hydrogen is provided especially OH, NH ₂, NHR-or-SH, wherein R-is the alkyl that contains up to 8 carbon atoms; Or the group of other crosslinking activitys is provided, especially epoxy, (methyl) acrylate, cyanate, isocyanic ester, acetylene or ethylidene are as vinyl, allyl group or maleimide, acid anhydride, oxazoline with contain the monomer of saturation ratio.

Wherein said at least a aromatic polymer comprises reactive side group and/or end group, is preferably selected from reactive heteroatoms, contains heteroatomic group or crosslinked group, as above-mentioned R is defined.

Specifically, described at least a aromatic polymer comprises at least a poly aromatic sulfone, and described poly aromatic sulfone contains repeating unit that ehter bond connects, maybe can also contain the repeating unit of thioether keyed jointing, and described unit is selected from-(PhAPh) _n-and or in addition-(Ph) _a-;

Wherein A=CO or SO ₂, Ph is a phenylene, n=1-2 can be a mark, a=1-4, preferred a=1,2 or 3, and can be mark, when a surpassed 1, described phenylene connected by single chemical bond is linear, or by-CO-or-SO ₂-in addition divalent group connects, and perhaps directly condenses or condenses by loop section, and this loop section is dialkylaminobenzoic acid, (mixing) aromatic base or cyclic ketones, acid amides, imide, imines etc. for example.

Aromatic polymer preferably comprises polyethersulfone, the more preferably mixture of the mixture of polyethersulfone and the polyether ethersulfone that is connected repeating unit, wherein phenylene be between or right-phenylene, preferably right-phenylene, this phenylene connects by the divalent group beyond single chemical bond or the sulfone is linear, or condenses." mark " is meant the mean value that contains the unitary given polymer chain with different n or a value.

Repeating unit-(PhSO ₂Ph)-preferably always be present in the described at least a polyaryl sulfone, ratio is average at least two described unit-(PhSO ₂Ph) _n-being present in each polymer chain with order, described at least a polyaryl sulfone contains reactive side group and/or end group.

In addition, in the polyaryl sulfone polymkeric substance, the relative proportion of described repeating unit is average at least two unit-(PhSO ₂Ph) _n-adjacent being present in each polymer chain, preferably 1: 99-99: in 1 scope, especially 10: 90-90: in 10 scopes.This ratio generally is at 75-50 (Ph) _aIn the scope, all the other are-(PhSO ₂Ph) _n-.In preferred polyaryl sulfone, the unit is:

(I)XPhSO ₂PhXPhSO ₂Ph(″PES″)，

(II)X(Ph) _aXPhSO ₂Ph(“PEES”)；

Wherein X is O or S, at different units can be different, the ratio of I and II is preferably 10: 90-80: 20, especially be preferably 10: 90-55: 45, more preferably 25: 75-50: 50, perhaps this ratio is 20: 80-70: 30, more preferably 30: 70-70: 30, most preferably be 35: 65-65: 35.

The preferred relative proportion of polyaryl sulfone repeating unit can be used SO ₂Weight percentage represent, be defined as 100 * (SO ₂Weight)/weight of average repeating unit.Preferred SO ₂Content is at least 22%, preferred 23-25%.When a=1, this ratio corresponding to PES/PEES was at least 20: 80, was preferably 35: 65-65: 35.

Aforementioned proportion only refers to the unit mentioned.Except these unit, polyaryl sulfone can also contain up to 50 moles of %, especially up to other repeating units of 25 moles of %: preferred SO ₂Content range (if using this phraseology) then be applicable to whole polymkeric substance.These unit can be for example to have following formula:

-Ar-A-Ar-

Wherein A be direct key, oxygen, sulphur ,-CO-or bivalent hydrocarbon radical.When polyaryl sulfone is the nucleophilic synthetic product, its unit can come from for example one or more bis-phenols and/or corresponding dithiol or phenol-mercaptan, they are selected from quinhydrones, 4,4 ' dihydroxyl phenylbenzene, Resorcinol, dihydroxy naphthlene (2,6 and other isomer), 4,4 '-dihydroxy benzophenone, 2,2 ' two (4-hydroxyphenyl)propanes and methane.

If the use dithiol, it can form in position, promptly for example following dihalide can with alkali metal sulfides or polysulfide or thiosulfuric acid reactant salt.

These other unitary other examples have following formula:

-Ph-Q(Ar-Q′) _n-Ph-

Wherein Q and Q ' can be identical or different, are CO or SO ₂, Ar is a divalent aryl, n is 0,1,2 or 3, condition be when Q be SO ₂The time, n is not 0.Ar is at least one divalent aryl preferably, is selected from phenylene, diphenylene or triphenylenyl.Concrete unit has following formula:

-Ph-Q-[(-Ph-) _m-Q′-] _n-Ph-

Wherein m is 1,2 or 3.When polymkeric substance is nucleophilic synthetic product; such unit can come from one or more dihalide; for example be selected from 4; 4 '-dihalo benzophenone, 4; 4 ' two (4-chloro-phenyl-alkylsulfonyl) hexichol, 1; 4 two (4-two (4-halogeno-benzene formyl radical)) benzene and 4,4 ' two (4-halogeno-benzene formyl radical) hexichol.

Certainly they can partly come from corresponding bis-phenol.

Aromatic polymer can be the nucleophilic synthetic product of halogenated phenols and/or halogeno-benzene thiophenol.In any nucleophilic was synthetic, halogen atom (if chlorine or bromine) can activate under the copper catalyst existence condition.

If halogen atom is activated by electron-withdrawing group, so such activation does not usually just need.In any case, fluorochemical is active bigger than muriate usually.The nucleophilic of any aromatic polymer is synthetic all preferably to carry out under one or more alkaline metal salt existence conditions, and alkaline metal salt is KOH, NaOH or K for example ₂CO ₃, surpass stoichiometric 10 moles of %.

Polymkeric substance can characterize with MW, and MW is generally defined by Mn, MW peak and other modes, is measured by nmr and gpc usually.Preferred select up to 70000 for example the polymkeric substance of 9000-60000 carry out toughness reinforcing, in this case, the number-average molecular weight Mn of aromatic polymer is suitable in the 2000-25000 scope, preferably in the 2000-20000 scope, more preferably 5000 or the 7000-18000 scope in, most preferably 5000 or the 7000-15000 scope in.

Aromatic polymer preferably has lower molecular weight.It also preferably contains side group or end of the chain chemical group at chain, and these groups can react voluntarily by chemical groups similar or different in non covalent bond and the polymkeric substance, form more high-molecular weight title complex.These can be for example hydrogen bond, London logical sequence power, charge-transfer complex, ionic linkage or other secondary or physical bonds.Non covalent bond is hydrogen bond or London force preferably, decompose regeneration lower molecular weight precursor aromatic polymer in these non covalent bonds.This aromatic polymer preferably contains side group or terminated radical, these groups can with the radical reaction in the compositions of thermosetting resin, form covalent linkage.Such group can obtain by monomeric reaction, or obtains by the follow-up conversion of the polymer product before or after separating.Preferred group has following formula:

-A′-Y

Wherein A ' is a bivalent hydrocarbon radical, preferred fragrance base, Y be can to epoxide group or to solidifying agent or to other polymer molecules on the group of similar radical reaction.The example of Y provides the group of active hydrogen, especially OH, NH ₂, NHR ' or-SH, wherein R ' is the alkyl that contains up to 8 carbon atoms, or provide the group of other crosslinking activitys, especially epoxy, (methyl) acrylate, cyanate, isocyanic ester, acetylene or ethylidene are as ethene allyl group or maleimide, acid anhydride, oxazoline with contain the monomer of saturation ratio.Preferred end group comprises amine and hydroxyl.

Of the present invention one especially favourable aspect, the polymkeric substance of flexible polymer element can have lower molecular weight, but it is suitable for reaction when solidifying, for the needs of toughness reinforcing grade effectively provide more high molecular, as described in the GB0020620.1 of pending trial, its content quotation is incorporated into this.Because it has further alleviated the high viscosity problem, so be very favorable.Specifically, polymkeric substance can comprise the chain of at least a aromatic polymer or their combination chain, also contain at least a chain and connect component, wherein said at least a aromatic polymer comprises the polymer chain of number-average molecular weight (Mn) in the first scope 2000-11000 especially 3000-9000 scope, and characterize described at least a aromatic polymer with the yield temperature of polymkeric substance and be connected a kind of in the component with at least a chain and comprise at least a reactive terminal group, and other comprise at least two kinds of connecting portion reactive terminal group Y and chain connecting portion, and Z is selected from OH, NH ₂NHR-or-SH, wherein R is the alkyl that contains up to 8 carbon atoms, epoxy, (methyl) acrylate, cyanate, isocyanic ester, acetylene or ethylidene such as vinyl or allyl group, maleimide, acid anhydride, acid, oxazoline and the monomer that contains degree of unsaturation, it is characterized in that many end groups are suitable for connecting temperature and connecting portion reaction at the chain that surpasses the polymer flow temperature, form number-average molecular weight (Mn) at the second scope 9000-60000, especially the polymer chain of the connection in the 11000-25000, this second scope has surpassed aforementioned first scope, is thermoplastic substantially in nature.

Yield temperature is defined as such temperature, and under this temperature, polymkeric substance reaches suitable flow state, and feasible polymer chain to a certain degree can move lines up row, so that react.Yield temperature is preferably corresponding to aromatic polymer dissolved solvent temperature.

Chain connects temperature and is defined as such temperature, and under this temperature, the reaction of polymer chain end begins.Chain connects temperature and preferably is higher than the processing temperature of product, so that remove solvent, improves the humidity of prepreg, and this can make the better quality of prepreg, and has the characteristic that is easier to handle.Chain connects temperature preferably corresponding to gelation temperature or solidification value.

Chain connects component and is preferably selected from the component with following formula:

B (Z) _nWherein B is oligopolymer or main polymer chain, or the fat of 1-10 carbon atom, alicyclic ring or aromatic hydrocarbon, one-tenth can comprise heteroatoms N, S, O etc., also maybe can be substituted, or the nuclear of C, O, S, N or transition metal or singly-bound, n is an integer, is selected from 2-10000, preferably 2-8 or 5-500 or 500-10000.

Thus, it is evident that, for example the methacrylic ester end polymer is connected the autoreaction between the component with chain, or the maleimide end polymer is connected the autoreaction between the component with chain, or the autoreaction that the oxazoline end polymer is connected with chain between the component is contingent, all within the scope of the invention.

One preferred embodiment in, the reactive terminal group is a hydroxyl, and corresponding to the connecting portion functionality that is epoxy, thus, their reaction is with regard to the β hydroxyl ehter bond in the polymkeric substance that has formed number-average molecular weight with desired hydroxyl or epoxy end group and be improved.In addition, the reactive terminal group is NH ₂, the connecting portion functionality is an acid anhydride, their reaction just forms and has NH thus ₂Or the imide bond in the polymkeric substance that is improved of the number-average molecular weight of acid anhydride end group.In addition, the reactive terminal group can also be NH ₂, the connecting portion functionality is a maleimide.Also can use the mixture of above-mentioned substance, make mixed structure, comprise the combination of many reactive terminal group-connecting portions.

The preferred component that connects comprises polyfunctional epoxy resin, amine and especially triazine and acid anhydride.Suitable Resins, epoxy and amine are selected from the resin of following resinous substrates, are preferably selected from MY0510, Epikote828 (O (CH ₂CH) CH ₂OPh) ₂C (CH ₃) ₂, the Cymel class of epoxide comprises Cymel 0510, benzophenone tetracarboxylic dianhydride (BTDA) (O (CO) ₂Ph) ₂CO and maleic anhydride.

The flexible member may that preferably comprises two or more polymkeric substance comprises the blend or the multipolymer of amorphous polymer or the blend of amorphous and semi-crystalline polymer or multipolymer.This reduces and still keeps good end properties for example many block component of solvent resistance are especially favourable for preparing processing temperature.

In one side more of the present invention, some known or new methods are provided, for example comprise vestige etch or mechanical stretching fluoropolymer resin melt, the phase intermediate processing for example floods, evaporation, solvent cast, by the use of thermal means and wet method, prepare above-mentioned flexible polymer element, or form parts and polymerization by the monomer whose precursor.

Fiber or film member preferably obtain like this, resin melt is continuously extruded to spool, form film or spinning with known method in the synthetic yarn fabric manufacturing by mechanical thermal stretch, polymer melt more preferably is provided, and extract out with component shape, carry out heat and mechanical stretching, this stretching can make the polymer chain orientation, makes parts have elasticity, be easy to dissolving, cooling then, desired distance, for example 50-500mm preferably stretch in air.Preferably, use rate of pumping to be controlled to be to provide desired polymer line density (Tex), polymer melt is extracted out the die head of by having number required hole or slit for example up to the pump of 180Tex.

Parts can be by micronization or polymkeric substance, particle or other extrudates etc. of micronization are not made.Fiber preferably is made for has the nearly multifilament of 20 identical or different polymer filaments, and it is extracted out by molten polymer, and cooling and as requested or twisting is more then heated and stretched.Multifilament is easy fracture more not, when selecting the long filament and the twist/rice, has one to trade off between higher-strength and low flexibility.Twisting is to be conventionally used for preparation suture fiber, offsets the unaccommodated natural twist and anti-fracture.

In still another aspect of the invention, for curable compositions provide the structural support body is a carrier, it comprises at least one above-mentioned flexible polymer element, maybe can also have structure unit together, this structure unit is fortifying fibre preferably, wherein said at least one flexible polymer element exists with solid-state form, and be lower than the temperature that curable components significantly begins gelling and/or solidified temperature, when contact component dissolved in the resinous substrates component of curable compositions wherein, partial phase change was liquid at least.

When mentioning supporting structure herein and being carrier, what say is preferred and fortifying fibre monofilament or the multifilament fiber polymer element of combining closely for example on the physical form, supporting structure or carry intravital band and/or film be rendered as independent fiber or band or with fortifying fibre together, the form of supporting structure or carrier comprises fabric, net, Woven fabric, supatex fabric, the looping thing, prefabrication, bare cloth, reticulation, pile fabric, rove, prepreg, mixture or stratifide film or intertexture etc. or their mixture, or sew up, make, screw thread or similar type.The effect of suitable polymers parts is that other components (one or more) to supporting structure play a supportive role, or carrying fortifying fibre and/or resinous substrates, and desired curable compositions may any other component (one or more).Described supporting structure is that carrier can support or carry mutually, and at least one flexible polymer element also is enhanced fiber or additional resinous substrates supports or carries thus.

The structure of mentioning herein be that the enhanced fiber is meant known insoluble fiber in the industry, it strengthens mixture, the material of fortifying fibre for example is organic or inorganic polymkeric substance, carbon, glass, inorganic oxide, carbide, pottery or metal etc.

Supporting structure of the present invention is the physical aspect that carrier can have arbitrary number.

Supporting structure is that carrier can be known prefabrication form in the industry, but flexible polymer element wherein exists between the fortifying fibre with fiber or band, line up row or do not line up row or stitching, or exist with the multifilament form of soluble polymer fiber and fortifying fibre, described multiple line can be braiding, spun or looping; Flexible polymer wherein exists again or with membranaceous, and described film is put against fortifying fibre row, and adheres to it or flexing or physical bond otherwise.Especially advantageous forms comprises the supatex fabric of fortifying fibre and flexible polymer fibre suture, line up prefabrication or other structures of enhancing row or random and flexible polymer fibre, described prefabrication can be that sew up or acupuncture or remollescent to give bonding force, flexible polymer element presents inhomogeneously with respect to fortifying fibre in described other structures, so that around for example keyhole, fastener hole, heavily stressed plate etc., performances such as the performance of flexible polymer is for example toughness reinforcing are given in the part.

Under the structure or carrier situation of the comingling that contains flexible polymer element and fortifying fibre continuous, short or that cut off, at least one flexible member may is monofilament or the higher multifilament fiber of low twist/rice, also can be cut into comparable length and mixing simply.Contain woven fortifying fibre in case form the woven of 100% flexible polymer element fabric or the structure or carrier situation of woollen yarn knitting under, parts are monofilament or silk number less multifilament.When flexible member may was used as suture, it preferably had lower elongation %.In any case, structure or carrier can form in any suitable stage in preparation fabric base reinforce process.When it also can be for example forms the hole in the fabric that is combined into (prefabrication) or physics when sewing up the polycomponent parts, before injecting resin/solvent impregnated resin, in that to make fabric after-applied.

In a kind of preferred construction, above-mentioned supporting structure is that carrier preferably comprises in desired mode and arranges the structural fibers put and the fibrous flexible polymer element of suture form, it is suitable for taking place above-mentioned phase transformation, so that the part disperses or extensively is scattered in the curable compositions.Suitable is that supporting structure is that therefore carrier is exactly form of fabric, in the described fabric, structural fibers or fabric are arranged with random fashion, single shaft or multiaxis mode and are put, (being total to) is linear or (be total to) plane is arranged and put, and the fiber of flexible polymer element is routinely with suture form anchoring fiber or fabric or their molectron as requested.Stitching preferably includes and fixes fiber, fabric or their molectron with reaching the standard grade and rolling off the production line from opposite two sides.Described supporting structure is that carrier provides to the traceless suture of small part, and no vestige suture preferably is provided.Suitable is, flexible polymer element c is with for Tex, and (weight (gram) of the flexible polymer element of every 1000m structural fibers length) controlled amount provides, and following formula provides:

Tex _Fpe=(weight _Sf%x weight _Fpe%)/Tex _Sf

With fortifying fibre with keep polymkeric substance suture on the throne and sew up mixing and solidify the back, many technology are arranged.Specifically:

(i) carry out specific fiber row for directed enhancing and put (TFP), it comprises with desired direction row puts continuous reinforcing fiber, carrying out polymkeric substance then in multilayer sews up, this moment, the first via was stitched single line or structural fibers bundle, line or the structural fibers bundle of seam on overlapping taken turns in back one, one takes turns overlapping once more line that gets on of seam or fibrous bundle etc. subsequently again, goes down successively, the common like this mechanical property that just causes is generally poor, and the one side of the fabric that forms has the insoluble suture of many wheels;

(ii) suture line forms folded-seam, and form suture line along desired fold line this moment;

(iii) stitching causes sclerosis, and the position of suture in the flimsy material layer that intersect this moment is just very approaching, makes the rigidity and the planarity increase of fabric;

(iv) combination is sewed up, and for example will be orientated to this moment and on the throne stitching of the vertical fabric of second layer fabric;

(the v) stitching of non-crimps, this moment, the cross-level of fabric was sewed up by loosely, if it is too high to form smooth surface-stitching tension force, the surface coils of suture will make the fabric face arch camber on thickness direction, in addition, in non-damage test, suture can be mistakenly detected as defective, makes test result unreliable;

(vi) on carrying out with Kevlar fiber suture way thickness, the whole interlayer region of mixture sews up (TTF) with the Kevlar fiber, suture just can be held by for example trevira, make Kevlar suture softness, strengthen interlayer region, and reduce the possibility of demixing phenomenon.

Of the present invention one especially favourable aspect, all above-mentioned known sewing methods are provided, described method adopts the flexible polymer element of soluble fiber form to carry out in a usual manner.But described suture can dissolve when cure cycle begins to heat, and is scattered in the whole fabric, is only curing later on.The decline of mechanical property has just been avoided in such dispersion, in most cases, by improving the dispersion that for example comes from the toughening polymer that dissolves suture, has improved mechanical property.Therefore, one preferred embodiment in, the invention provides a kind of supporting structure is carrier, it comprises above-mentioned row puts and sews up, the present invention specifically provides seamless stitching.

Another aspect of the present invention, it is the method for carrier that the above-mentioned supporting structure of preparation is provided, it comprises provides at least one flexible polymer element, and above-mentioned fortifying fibre is provided again, and carries out combination in the mode of the physical bond that forms them.This combination is to be used to provide the close physical combination, can be undertaken by known method in the textile industry, for example by sew up, knitting, distortion, pin are perverse, woven, woollen yarn knitting, looping song, non-woven, comingling, arrangement, twisting, coiling, knotting, one-tenth line etc.

Supporting structure is that carrier can be made in a continuous manner, for example is fabric warrping, and this fabric can customize by sewing up and weave in desired mode, for example carries out cross and sews up, and avoids fabric adding the distortion in man-hour, and folded seam, directed enhancing etc. are provided.

The said structure fiber can be the fiber of staple fibre or cut-out, and average length is not higher than 2cm, for example about 6mm.In addition, fiber is successive preferably, can for example be fiber or Woven fabric that unidirectional row puts, and promptly composite materials comprises prepreg.Can adopt short and/or staple fiber and long stapled combination.Fiber can be starching or not starching.Fortifying fibre can add with general concentration with 5-35 weight %, preferably at least 20 weight %.For structural applications, preferably use continuous fibre for example glass fibre or carbon fiber, especially 30-70 volume %, more specifically 50-70 volume %.

Fiber can be organically, rigid polymer polyparaphenylene's terephthalamide for example especially, or inorganic.In inorganic fibre, can use glass fibre for example " E " or " S ", or aluminum oxide, zirconium white, silicon carbide, other ceramic compounds or metal.A kind of most suitable fortifying fibre is an especially graphite fibre of carbon fiber.Those fibers of those fibers that graphite fibre of the present invention is the commodity that provide of Amoco T650-35, T650-42 by name and T300, commodity T800-HB by name that Toray provides and commodity AS4, AU4, IM8 and IM7 and HTA and the HTS fiber by name that Hercules provides are provided in discovery.

Organic or carbon fiber is preferably used material starching or the not starching compatible with the present composition, compatible meaning is to dissolve in the liquid precursor composition, and disadvantageous reaction can not take place, or be adhered on fiber of the present invention and the thermoset/thermoplastic compounds.Especially carbon fiber or graphite fibre Resins, epoxy precursor starching or not starching.Preferably with being adhered to the material starching that can be adhered to again on the fiber on the polymer composition, example is the organo silane coupling agent that is applied on the glass fibre to inorganic fibre.

Provide a kind of curable compositions more on the one hand of the present invention, it comprises above-mentioned flexible polymer element or supporting structure is carrier and curable resin matrix, together with the fortifying fibre that maybe can have, catalyzer, solidifying agent, additive filler etc. for example.

Matrix resin is thermosetting resin preferably, can be selected from Resins, epoxy, the addition polymerization resin is di maleimide resin especially, formaldehyde condensation resins is the formaldehyde phenolic resin especially, cyanate ester resin, isocyanate resin, the mixture of two or more in resol and they preferably is selected from the Resins, epoxy that following list or many glycidyl derivatives form by one or more: aromatic diamines, the fragrance primary monoamine, amino phenol, polyhydroxy phenol, polyvalent alcohol, poly carboxylic acid, cyanate ester resin, benzoglyoxaline, the polystyrene yl pyrimidines, polyimide or resol etc. or their mixture.The example of addition polymerization resin is acrylic acid derivative resin, Vinylite, dimaleimide and unsaturated polyester.The example of formaldehyde condensation resins is urea, melamine and phenol.

Thermoset resin substrate more preferably comprises at least a in epoxy, cyanate or the resol precursor, and it at room temperature is liquid, for example among EP-A-0311349, EP-A-0365168, EP-A-91310167.1 or the PCT/GB95/0130303 description is arranged.Thermosetting resin is more preferably Resins, epoxy or cyanate ester resin or their mixture.

Resins, epoxy can be selected from N, N, and N ', N '-four glycidyl group diaminodiphenyl-methane (for example " MY9963 ", " MY720 " or " MY721 ", CibaGeigy sell), 50 ℃ viscosity is 10-20Pas; (MY721 is low viscosity type MY720, is specified in higher use temperature); N, N, N ', N '-four glycidyl group-two (4-aminophenyl)-1,4-two different-propylbenzenes (for example Epon 1071, and ShellChemical Co. sells), 110 ℃ viscosity is the 18-22 pool; N, N, N ', N '-four glycidyl group-two (4-amino-3,5-3,5-dimethylphenyl)-1,4-diisopropyl benzene (for example Epon 1072, and Shell Chemical Co. sells), 110 ℃ viscosity is the 30-40 pool; The triglycidyl ether of para-aminophenol (for example " MY0510 ", Ciba-Geigy sells), 25 ℃ viscosity is 0.55-0.85Pas, and 25 ℃ viscosity is preferably 8-20Pas, and preferably it constitutes at least 25% of used epoxy component; The material of bisphenol A diglycidyl ether base, for example 2,2-two (4,4 '-dihydroxy phenyl) propane (for example " DE R661 ", Dow sells, or " Epikote 828 ", is sold by Shell), novolac resin, 25 ℃ viscosity is preferably 8-20Pas; The glycidyl ether of phenol novolac resin (for example " DEN 431 " or " DEN 438 ", Dow sells), the preferably kind of its low viscosity class of use in the preparation present composition; Diglycidyl 1,2-phthalic ester, for example GLY CEL A-100; The 2-glycidyl derivative (Bisphenol F) of dihydroxyl ditan (for example " PY306 ", Ciba Geigy sells), it is the low viscosity type.Other Resins, epoxy precursors comprise alicyclic ring, for example 3 ', 4 '-epoxycyclohexyl-3, the interior material of " Bakelite " scope of 4-epoxycyclohexane carboxylate (for example " CY179 ", Ciba Geigy sells) and Union Carbide Corporation.

Cyanate ester resin can be selected from one or more in compound, oligopolymer and/or paracyanogen acid esters and their combination that general formula is NCOAr (YxArm) qOCN, wherein Ar is list or condensed aromatic base or aromatic base that replaces and their combination, and just between them, have, and/or the nuclear of contraposition connect, x=0-2, m and q each=0-5.Y is a connector element, be selected from oxygen, carbonyl, sulphur, sulfur oxide, chemical bond, just be connected, and/or the aromatic base of contraposition, and/or CR ₂, R ₁And R ₂Be hydrogen, haloalkane, for example aromatics of fluoroalkane and/or replacement and/or hydrocarbon unit, wherein said hydrocarbon unit is single or multiple connections, and by each R of 20 carbon atoms nearly ₁And/or R ₂And P (R ₃R ₄R ₄' R ₅) composition, wherein R ₃Be alkyl, alkoxy aryl or hydroxyl, R ₄' can with R ₄Identical, be single bonded oxygen or chemical bond, R ₅Be two key oxygen or chemical bond, or Si (R ₃R ₄R ₄' R ₆), R wherein ₃, R ₄, R ₄' definition and top P (R ₃R ₄R ₄' R ₅) in identical, R ₅Definition and above-mentioned R ₃Identical.Commercially available cyanate comprises the cyanate of the novolac resin that phenol/formaldehyde forms or the derivative of its Dicyclopentadiene (DCPD), an one example is XU71787, is sold and low viscosity cyanate L10 (Lonza for example by Dow Chemical Company, Ciba-Geigy, bisphenol derivative).

Resol can be selected from any aldehyde condensate resin that is formed by following aldehyde and phenol, and described aldehyde is for example formaldehyde, acetaldehyde, phenyl aldehyde or furfural, and phenol is for example phenol, cresols, dihydric phenol, chlorophenol, C _1-9Alkylphenol is phenol, 3-and 4-cresols (1-methyl, 3-and 4-hydroxybenzene), pyrocatechol (2-hydroxyl phenol), Resorcinol (1, the 3-dihydroxy-benzene) and Resorcinol (1, the 4-dihydric phenol) for example.Preferred resol comprises cresols and phenol novolak.

Suitable di maleimide resin is heat-setting resin, and it contains maleimide amino as reactive functionalities.Except as otherwise noted, term dimaleimide used herein comprises list, two, three, four and the more maleimide of high functionality and their mixture thereof, except as otherwise noted.Preferably average functionality is about 2 di maleimide resin.For example make by methyl maleic anhydride and fragrance or aliphatic diamine or polyamines reaction by the maleic anhydride of maleic anhydride or replacement for Ding Yi di maleimide resin like this.For example in United States Patent (USP) № 3018290,3018292,3627780 and 3770691 and 3839358, can find the example of preparation.Also can use the n unit imide resin of related intimate, it be similarly by two or polyamines make, but maleic anhydride by the maleic anhydride of maleic anhydride or replacement and diamines for example the Diels-Alder reaction product of cyclopentadiene replace.Herein with claims in the term dimaleimide that uses should comprise n unit imide resin.

Preferred two or the polyamines precursor comprise fat and aromatic diamines.Aliphatic diamine can be straight chain, branching or cyclic, can contain heteroatoms.Many examples of this aliphatic diamine can find in the last document that draws.Especially preferred aliphatic diamine is hexanediamine, octamethylenediamine, decamethylene diamine, dodecyl diamines and trimethylammonium hexanediamine.

Aromatic diamines can be monokaryon or multinuclear, can also contain the fused rings system.Preferred aromatic diamines be phenylenediamine, tolylene diamine, various methylene-dianiline especially 4,4 '-methylene-dianiline, naphthylene diamine, the various formula H that meets ₂N-Ar[X-Ar] _nNH ₂Or the oligopolymer of the aminoterminal polyarylene similar to this formula, wherein each Ar can be separately single-or multinuclear arylidene free radical, each X can be separately-O-,-S-,-CO ₂-,-SO ₂-,-OCO-, C ₁-C ₁₀Low alkyl group, C ₁-C ₁₀Haloalkyl, C ₂-C ₁₀Rudimentary alkylene oxide group, inferior aryloxy, polyoxyalkylene or polyoxy phenylene, wherein n is integer and primary amino alkyl end capped two and the many siloxanes of about 1-10.

What be particularly useful is dimaleimide " eutectic " resin compound, and it contains several dimaleimides.Such mixture has the fusing point that is significantly less than single dimaleimide usually.The example of this mixture can find in United States Patent (USP) № 4413107 and 4377657.Several such eutectic mixtures can have been bought.

Be preferably, flexible polymer element and dissolved matrix are elected " dissolving to " as, and requirement is not only to dissolve under required time and temperature, and has good matrix injectivity, dispersiveness and form, for example be separated and do not have vestige and disperse, if requirement.Suitable dissolving can be injected and rapidly-soluble low viscosity matrix resin well to comprising, and this matrix resin and parts resin compatible.In addition, if require to be separated, so also can use the lower resin of consistency to strengthen mechanical property.When above-mentioned different performance can not be provided by single kind resin, can use the combination of viscosity different resins, every kind of resin all works to above-mentioned every kind of performance.

In curable compositions, the existence form of flexible polymer element can be in a known way with the fiber in the prepreg of matrix resin dipping, hands over the film of knot with matrix membrane, perhaps with the porous or the foam materials film of dippings such as matrix resin.

When flexible polymer element comprised liquid high-viscosity polymer or its precursor, the present invention was especially favourable.Described curable compositions preferably comprises the heat-curable matrix resin of at least a foregoing curable, also maybe can comprise at least a thermoplastic matrix resin.

Such composition can make the end article improved performance, and mixture just can higher specification provide thus.Usually only add additive for this reason or increase certain components contents.But, there is a problem in this way, promptly the content of high viscosity resins can be brought up to and go beyond the limit, and reach the high quality blend that described limit just no longer can obtain to contain other composition component, and other materials or the additive many performances that can not give this resin.In preparation high strength low weight engineering materials, during with adhesive thermoplastic resin especially like this.

Comprise at resinous substrates under the situation of at least a thermoplastic resin, curable compositions just contains the thermoplastic polymer of high level, therefore thermoplastic resin just exists with first content with liquid state as matrix components, in addition, exist with second content with at least a solid-state flexible polymer element form.

The thermoplastic resin component is preferably contained at least a thermoplastic polymer, can be the blend of the thermoplastic polymer that exists with first or second content or the identical or different thermoplastic polymer that exists with first and second content.

The thermoplastic resin component can exist with any suitable content.Preferably with first content of liquid state, promptly extremely can there be preferred 1 weight %-15 weight %, more preferably 5-12.5 weight % in the thermoplastic resin component with resinous substrates blend and/or the content that is impregnated in the fortifying fibre from 1 weight %; And, promptly there are preferred 1-50 weight %, more preferably 5-30 weight %, most preferably 5-20 weight % to any amount that is suitable for required purposes from 1 weight % with solid-state second content.Therefore, thermoplastic resin component's total content can account for the 2-65 weight % of the present composition.

The unforeseen circumstances of this embodiment of the invention comes from such fact, it is the form that we find to be provided as by the part with the thermoplastic resin component flexible polymer element, for example can be dissolved in the interior fiber of matrix resin, film etc., the thermoplastic resin component of high level etc. just can be provided in curing composition.Thus, it just can equably and can be present in the curable compositions controllably, and disperses equably by above-mentioned partial phase change at least, forms the blend polymer with the performance that requires.

In addition, also be that this polymer elements that can undergo phase transition in thermoset resin substrate that we have found earlier can specifically be to undergo phase transition in thermoplasticity-thermoset resin substrate in containing the resinous substrates of thermoplastic resin unexpectedly.In addition, also be unexpectedly, the composite properties that contains the higher amount thermoplastic resin component that is obtained by this mode increases, and this is the higher result of thermoplastic resin content.

Solidifying agent is suitable for selecting from any known thermoset solidifying agent, epoxy hardener for example, as described in EP-A-0311349, EPA91310167.1, EP-A-0365168 or PCT/GB95/01303, its reference in content is incorporated into this, for example for each amino, molecular weight is up to 500 aminocompound, for example derivative of aromatic amine or guanidine.Concrete example is 3,3 '-and 4,4 '-diamino diphenyl sulfone (" DDS " of purchase), methylenedianiline, two (4-amino-3, the 5-3,5-dimethylphenyl)-1,4-diisopropyl benzene (with EPON1062 available from Shell Chemical Co), two (4-aminophenyls)-1,4-diisopropyl benzene (with EPON1061 available from Shell Chemical Co), 4-chlorobenzene-N, N-dimethyl urea is monuron for example, 3,4-dichlorobenzene-N, N-dimethyl urea be Diuron Tech and dicyano diamide (with " Amicure CG1200 " available from Pacific Anchor Chemical) for example.If desired, for example aliphatic diamine, acid amides, carboxylic acid anhydride, carboxylic acid and phenol of the standard epoxy hardener that also can use other.If use the phenol phenolic novolac as main heat-curable component, so formaldehyde produce agent for example vulkacit H (HMT) generally as solidifying agent.In a preferred embodiment of the present invention, flexible polymer element comprises aromatic polymer, and curable compositions also comprises the catalyzer of aromatic polymer.In this case, used curing catalysts also preferably comprises the Lewis acid with amine functionality except comprising conventional catalyst, or promptly replaces conventional catalyst with this Lewis acid, and as described in the GB0002145.1 of pending trial, its content quotation is incorporated into this.Catalyzer preferably has following formula:

LXn.R wherein LXn is a Lewis acid, and R is an amine.L is preferably selected from the element of periodic table of elements IIb, IIIb and VIII family, and X is a halogen atom.

Catalyzer preferably includes BF ₃, AlF ₃, FeF ₃, ZnF ₂As Lewis-acidic components and uncle or secondary aliphatic amide or aromatic amine for example mono aminoethane, dimethylamine, benzylamine or piperidines.

Provide a kind of preparation foregoing curable method for compositions more on the one hand of the present invention, it comprises being that carrier contacts with resinous substrates by the dipping that interweaves, injection or methods such as injection, mixing with above-mentioned flexible polymer element or supporting structure for example.

Then, described composition can be before solidifying, in a known way with curable compositions in miscellaneous part for example fortifying fibre or other composite component for example metal or polymkeric substance or other objects or structure are together arranged and are put.

In the non-limiting example mode the concrete purposes that can use the invention described above flexible polymer element is described below.

Curable compositions of the present invention can be used for preparing fabric, described fabric can comprise polymkeric substance and other resinous substrates polymkeric substance that comes from flexible polymer element, and for example high molecular weight polyesters, polymeric amide are as the combination of nylon etc. (they be used for forming " bare cloth " in the mixture industry).These " bare cloths " are not complete films, but have unlimited weaving structure, like this, and just can be as the carrier of binder resin component." bare cloth " just is called binder film with the combination of resin Composition.Such film can be used for the composite structure body is glued together, and mixture is adhered on the metal structure.Flexible polymer element such as soluble fiber as " bare cloth " part can dissolve when tackiness agent solidifies, and then are separated, and form selected predetermined form.Will improve the adhesion property of resin like this, and increase the cohesive performance of resin substrate surface.Select flexible polymer element that tackiness agent bonded environmental resistance is improved suitably.

Find that these another kind of purposes that are called " bare cloth " are as intertexture, thermoplastic resin is introduced the interlayer region of conventional prepreg.Bare cloth also can be used for intervening goods, and in this case, the weaving structure that opens wide of bare cloth can make the injection/injection of thermosetting resin occur in whole prefabrication.This with add that to contain the continuous film situation that hinders resin flows different, this afterwards kind situation can produce the space thereby make mechanical property and environmental performance poor.

The present invention also can be applied to the moulding material field, and flexible polymer element this moment (one or more) can join in the formulation of molding compounds with the staple fiber form.This fiber design becomes can be kept perfectly, that is, when molding compounds during by injection moulding machine this fiber can not dissolve.This viscosity that just means molding compounds is lower usually, needs lesser temps and pressure to process moulding resin.This also means also can add other additives in resin, for example filler and fire retardant, and the viscosity of molding compounds is not had too bad influence.

Another purposes of the present invention is to be applied to continuous resin molding field.Soluble fiber can be continuous or discrete form, mixes making fiber dispersion with multiple thermosetting resin.This film of gained can be applied between the surface or layer of main structure reinforce then.

Another purposes of the present invention is the continuous film of preparation straight polymer, can be directly used in further processing to be suitable for specific end use.

Being used for soluble fiber of the present invention and any fortifying fibre combines with resinous substrates at any suitable stage of the course of processing.

Contain matrix resin or also contain the curable compositions of certain volatile solvent, can contact with flexible member may, comprise dipping, injection, injection etc. by several different methods.The softish polymeric film can become porous by solvent flashing, and dipping forms composite membrane then, for example is loaded with the film of adhesive resin, and perhaps multilayer film can adopt known technology to provide.

Injection can or be lower than the high temperature of known dissolving temperature in the industry in room temperature, and the scope of room temperature to 100 ℃ is preferably carried out in room temperature to 75 ℃ scope more fortunately, makes resin viscosity suitable.Injection can be used bag, heart type and/or mould with known prepreg or prefabrication form, also uses flute to wait sometimes and assists to flow, and this is known in the industry.Be fit to 2-300 minute inject time, and preferred 2-120 minute, for example 2-30 minute.

Preferably make basic successive fiber by contacting, prepare fibre-reinforced composites with such resin combination.Formed impregnated fabric reinforcement can use separately or and other materials, for example other many identical or different polymkeric substance or resin precursor or mixture together use, and form moulded products.This technology has detailed description in EP-A-56703,102158 and 102159.

Another kind method comprises by for example mold pressing, extruding, melt cast or Strip casting, not completely crued resinous substrates composition is configured as film, be enough to make under the condition of mix flow and impregnation of fibers, the film of gained is laminated to fiber enhancer and thermoplastic fibre, on (for example being supatex fabric pad, Woven fabric or basic successive fiber) than staple fibre, and the sandwich that solidify to form.

A plurality of layers of fabric reinforcement through flooding, especially use EP-A-56703, one or more described methods are (in these methods in 102158 and 102159, also contain thermoplastic fibre) make can pass through heat and pressure, for example use thermal compressor, vacuum moulding or mold pressing or use hot-rolling, in the temperature that is higher than more than the thermosetting resin cured temperature, take place if perhaps solidify, in the temperature that is higher than more than the second-order transition temperature of mixture, at least 180 ℃ easily, generally up to 200 ℃, and, preferably under the pressure in 1-10 crust scope, stack especially surpassing 1 crust.

Formed multilayer laminated thing can be anisotropic, wherein fiber is continuous and unidirectional, substantially orientation parallel to each other, or it is quasi-isotropic, fiber is orientated at an angle with respect to the upper and lower in each layer, being 45 ℃ of orientations easily in most quasi-isotropic sandwich, is 30 ℃ or 60 ℃ or 90 ℃ or between the angular orientation between them but can for example be.Can use the sandwich of orientation between anisotropy and isotropic combination.Suitable sandwich contains at least 4 layers, preferably at least 8 layers.Depend on the number of the layer purposes of sandwich, for example needed intensity, sandwich can contain 32 layers or even more, for example hundreds of layers suit.Woven fabric be quasi-isotropic or between anisotropy and quasi-isotropic between example.

In addition, sandwich can also be a single or multiple lift, comprises that the fortifying fibre of putting with shop above one or more layers comes directed the enhancing, with soluble fiber (TFP) stitching on the throne.Sandwich can assemble in the mode that is shaped, the two-layer fabrics orientation that can be perpendicular to one another for example, formation upholder etc., and with soluble fiber in former stitching.

The liquid molding composition that curable compositions provided by the invention is preferably obtained by known liquid molding method in the industry, wherein flexible polymer element or the above-mentioned supporting structure that comprises fortifying fibre (doing) and at least one flexible polymer element are that carrier is put into bag, mould provides prefabrication, fiber and parts that resinous substrates then is added to the method for direct injection/injection.

In one side more of the present invention, a kind of method of cure curable compositions is provided, it comprises provides above-mentioned composition, provide other components to comprise other enhanced matrix components, additive etc., be suitable for time that flexible polymer element is undergone phase transition for one section in pyroprocessing, be suitable for making curable components generation gelling and/or solidified time one section of pyroprocessing again, obtain the solidified mixture.

Other fabric reinforcement or resinous substrates also can add supporting structure in conjunction with it before matrix immobilized.

Prefabrication preferably injects soft processing (RIFT), vacuum assisted resin transfer molding (VARTM), resin molding injection treatment technologies such as (RFI) by for example above-mentioned resin transfer molding (RTM), liquid resin injection (LRI), resin, and formation, injection/injection and curing are made.

Described method comprises suitably under reduced pressure injects additional resin matrix in advance, and the degassing then deflates and reduces the space.The degassing is to carry out under elevated pressures traditionally.

But, of the present invention one especially favourable aspect, we find, for above-mentioned specific support structures body is the situation of carrier body, the wherein arrangement of the fiber of two kinds of different diameters through adjusting causes to form ditch therebetween and be convenient to air flowing, and the degassing be carried out under just can or reducing pressure in room temperature.In this case, plate just can adopt for example vacuum-packed technique of RIFT or VARTM technology, injects, outgases and solidify, and does not need the external pressure of thermal compressor is applied on bag surface.

In this case, supporting structure is that carrier comprises and lines up the soluble of row, maybe can also have the fiber of two kinds of different mean diameters of structure.Therefore, supporting structure is a carrier multidirectional fabric suitably, wherein solvable or structural fiber with first diameter with than large-diameter fiber, arrange along the first diameter fibers conllinear, in whole composition, form longitudinal channel thus.

First diameter fibers is structural fibers normally, is carrier but this embodiment of the present invention also can comprise such supporting structure, and they have the soluble fiber of two kinds of diameters.Thus, just form raceway groove between them, part or all fiber dissolves after curing, and forming voidage and be 0 mixture is the virgin resin plate.

We are surprised to find that, supporting structure at this embodiment is in the carrier, the deaeration stage of the flexible polymer element of fibers form under initial room temperature or decompression still keeps fibre shape, and deflate in the slave plate, then, fibrolysis also disperses, can not leave vestige, make liquid phase component at the beginning gel with before solidifying, do not applying under the external pressure, denseization got up.If apply external pressure, only be to improve performance, but this structure can not need thermal compressor etc. when solidifying big plate for the first time, still particularly advantageous.

In this embodiment, the content of soluble fiber is 2-50 weight % suitably, preferred 2-40 weight %, more preferably 4-16 weight %.Soluble fiber Tex suitably is the multifilament of 30-160, against diameter 5-10 micron for example 6 or 7 microns structural fibers row put.

In addition, inject the stage at resin, described structure is favourable, and raceway groove wherein helps to inject fast and equably whole plate.

Another advantage is that this structure is improved injection, controls the resin flow forward position well.

Method of the present invention comprises suitably carries out up to 300 ℃, and for example 60-200 ℃, more preferably 75-150 ℃ high-temperature heat treatment reaches 45 minutes, and preferred 0.5-35 minute, in order to realize phase transformation.100-150 ℃ temperature is particularly suited for the low diffluent flexible polymer element of MW in the solvent of effective curable components, when existing, dissolved concentration undergoes phase transition being easy to, for not too easy dissolved flexible polymer element, temperature range is 150-300 ℃.In desired temperature range, select suitable high temperature, so that in required time, implement phase transformation, for example given flexible polymer element can 135-170 ℃ thermal treatment 2-10 minute, 125-135 ℃ 5-30 minute, or 105-125 ℃ 10-40 minute.

Phase transformation can be carried out under room temperature or the condition of high voltage corresponding with desired injection, the degassing and condition of cure.

This process stands high temperature after being included in phase transformation again, makes to begin gel or curing.Gel can carry out in corresponding to the temperature range of the Procuring of carrying out in a known way.After the gel, preferably carry out hot setting again, perhaps the composition of gel can cool off, carry out after fixing, if for example gel or curing are to carry out in thermal compressor or mould, composition just can take out in thermal compressor or mould, continues then to solidify in conventional baking oven under atmospheric pressure conditions.

Gel or solidify carries out suitably in a known way, by institute's requirement under high temperature and high pressure, carry out the suitable time, comprise heat-up rate and insulation.Suitable gel or cure cycle can be referring to the description and the embodiment of the cubage of flexible polymer element in the explanation composition corresponding to the conventional composition that contains same composition type and content.

For example, curing was preferably carried out 1-4 hour 180-400 ℃ of temperature.In addition, described method also is included in carries out after fixing under the appropriate condition, in order to improve the performance of Tg etc. and so on.

Can adopt above-mentioned catalyzer when gel or curing, this moment, elevated temperature can cause activation, and was cooled to below the activation temperature, and curing stops.

Described method can be controlled in real time, but for given composition, preferably by for example preparing sample, and finish gel or solidify after for example analyse solution and dispersion liquid with Raman's spectrogram five equilibrium, be scheduled to suitable reaction times and temperature.

In one side more of the present invention, one cover parts are provided, the dissolving that comprise above-mentioned flexible polymer element, is suitable for dissolving flexible polymer element is a carrier or as the fortifying fibre that has of separating component, together with any other fortifying fibre, matrix, monomer or polymkeric substance, solidifying agent etc. to resinous substrates, as supporting structure.

In one side more of the present invention, a kind of solidified mixture or resinite are provided, the structural fibers that it comprises the solidified resinous substrates and can have, with the dispersive cured polymer that comes from above-mentioned soluble flexible polymer element, exist mutually with separation mutually total or that from resinous substrates, separate.

Of the present invention more on the one hand, provide a kind of according to selection such as classification, molecule type or be mixed with the method for the resinous substrates that helps to dissolve above-mentioned flexible polymer element.The molecular weight of polymkeric substance is high more, and dissolving is just big more to resinous substrates required consistency or solvency action, and for example, the multi-functional epoxy is just effective than list or two sense epoxies, and phenol is more effective than cyanate or BMI.

In one side more of the present invention, just can provide a kind of formed composite structure of making without mould, it comprises each assembled part, wherein above-mentioned flexible polymer element is through weaving or sewing up into, its effect is to produce mechanical property and/or produce the enhancing of planarity, folded seam, hinged joint and bolt hole, directed enhancing etc., be used for assembling, these each several parts assemble as suture with flexible polymer element, and during injecting resin that structure is fixing on the throne.The ad hoc structure body that can provide comprises the reticulation prefabrication and is used for the compoboard of purposes such as aviation, automobile, submarine, wind energy.

In one side more of the present invention; above-mentioned flexible polymer element is provided; supporting structure is a carrier; prepreg or prefabrication; curable compositions or solidified mixture or resinite; they can be used for the preparation engineering mixture; be used for aviation; automobile; submarine; in the industrial use; be used for sports goods and paper mill; as roller; tinsel; the tackiness agent of usefulness such as electronic isolation thing; the usefulness of function or protectiveness coating; especially use as the serving textile that for example constitutes in the car body parts; as reinforcing membrane monofilm for example; as strengthening or being used for the preparation pipe as the silk thread winding; case; roller, or be used for for example bridge etc. of enhancement engineering structure.

The present invention is described with reference to the accompanying drawings.

Figure B1 (see above) illustrates the dissolving of fiber and is separated;

Figure B1a illustrates the dissolution time of fiber under differing temps of the present composition, and said composition comprises different epoxy matrix material components and different catalyst components;

Figure B1b illustrates dissolution time and the gel time curve under the differing temps, its explanation is in about 120 ℃-140 ℃ temperature, delta time (gel deducts dissolution time) is longer, and delta time is the time that all initial tensions and residual stress were all disappeared before resin gel;

Figure B2b-B2d illustrates the present invention's Raman's spectrogram of curing composition (composition shown in the figure B2a), and its explanation dissolved fiber is dispersed in the epoxy matrix material;

Figure B3a and B3b illustrate the mechanical property of fiber;

Figure B4 (see above) illustrates typical case's two phase morphologies of thermoplasticity/thermoset system;

Figure D1 has shown the structure of carbon fiber and soluble fiber Woven fabric;

Figure D2-D6 and D7a-D7c have shown the structure of above-mentioned multidirectional structure and suture and type of weave;

Figure E1a-E1c shown in wall use that polyester and soluble fiber sew up mutually in specie/multidirectional fabric of weight in, the dissolved comparison of the dissolving of polymer fiber suture of the present invention and soluble polyester suture;

What figure E2a-E2c had shown C warp-wise and C and soluble polymer broadwise mixes Woven fabric and the SEM photo of this fabric under differing temps, it shown when beginning not dissolving fiber and subsequently fiber be dissolved in intramatrical situation fully;

Figure F4a illustrates in the fabric shown in Figure 2, and aromatic polymer concentration is for the influence of the dissolution time of aromatic polymer fibrolysis in aromatic polymer/epoxy composite;

Figure G2 has shown used processing units, figure G2a-G2d has shown such plate, it uses the soluble fiber of arranging altogether with diameter small construction fiber to make, and processing under atmospheric pressure, by forming the raceway groove exhausted air because of the different diameter fibre array, the hole that it demonstrates formation is 0, has also compared the hole that forms in the plate that does not have soluble fiber.

With non-limiting way the present invention is described below with reference to some embodiment.

A part-supporting structure is the soluble fiber of carrier

The preparation of embodiment A 1-fiber

In this embodiment, use the following polymkeric substance shown in the Table I, prepare flexible polymer element of the present invention.

Polymkeric substance	Molecular weight	End group
				40∶60?PES∶PEES	9000	Amine
40∶60?PES∶PEES	12000	Amine
			40∶60?PES∶PEES	15000	Amine
40∶60?PES∶PEES	12000	Hydroxyl
			40∶60?PES∶PEES	7000	Chlorine
40∶60?PES∶PEES	9000	Chlorine
			40∶60?PES∶PEES	15000	Chlorine
100％PES(Sumitomo?5003P)	24000	Hydroxyl

In addition, also used following facing than the non-insoluble fiber of the present invention of the following polymer manufacture shown in the Table I:

Polymkeric substance	Molecular weight	End group
				100％PEEK	15000	Fluorine
Polyester PES
			Polyester TRIVERA

Polymkeric substance can be bought, or can be as preparation as described in EP311349, WO99/43731, GB0002145.1 or the GB0020620.1, and its reference in content is incorporated into this.

In the following embodiments, fiber laboratory scale and this prepared in one of two ways of industrial scale extrusion machine.

Embodiment A 2

Adopt the laboratory scale extrusion machine that polymkeric substance is spun into fiber

This step adopts the 15cm of the numbering 98013 of DSM manufacturing ³Miniature extrusion machine is implemented.

With each temperature fusing of fluoropolymer resin a scope, from the outward appearance of the stretch capability of system fiber, fiber and toughness/flexibility estimate quality of fiber.Back one performance initially is to observe fiber knotting simply and the ability that do not rupture is measured.

At 40: 60 PES: under the situation of PEES multipolymer, the temperature range of doing experiment was 270 ℃ to 320 ℃.

Polymkeric substance shown in the table is all estimated with regard to this preparation temperature scope, finds 290 ℃ of fibers that obtain best quality from the hot melt extruded machine of melt temperature.But only for 40: 60 PES: the PEES multipolymer is such situation.Under the situation of 100%PES, requiring minimum molten mass degree is 320 ℃.But,, require temperature up to 350 ℃ in order to reduce melt strength and can to pull out fine-fibered.

Embodiment A 3

Adopt the technical scale extrusion machine that the polymer spun silk is formed fiber of the present invention

For make this experiment can be on the technical scale extrusion machine smooth implementation, polymer powder is a granulated into granule very important.This can adopt the twin-screw extruder with three 35mm die heads, long 1400mm and 10 humidity provinces to carry out.Use following temperature distribution:

The district	Temperature (℃)
		Feeding district 1	Room temperature-100 ℃
Extrude district 1	}
		Extrude district 2	Increase
Extrude district 3	}250-375
		Extrude district 4	}
Extrude district n	}
1	Stable
		2	}250-375
3	}
		N	}

Screw speed is 230rpm, and the melt temperature of polymkeric substance is 294 ℃.The polymkeric substance of extruding water cooling at room temperature drops into cutter then.The mean diameter of gained granule is 3mm.

Then, be in 45mm, the long 1.26 meters single-screw extrusion machines with transfer of granules to die diameter.Use following temperature distribution:

The district	Temperature (℃)
		Extrude district 1	}
Extrude district 2	Increase
		Extrude district 3	}250-375
Extrude district n	}
1	}
		2	Stable
Pump	}250-375

The melt temperature of polymkeric substance is 295 ℃.The speed setting of pump is for forming desired Tex and desired breaking tenacity.Obtained the fiber of the present invention of four kinds of different Tex with different rate of pumpings, their Tex is in the 30-60 scope.Minimum screw speed is set at 11rpm, selects following process parameter, and the formation diameter is 30 microns a monfil:

Spinning die diameter * hole	0.3mm×100
		The cooling bath temperature	60C
The first draw unit speed	Do not use
		The first orientation oven temperature	25C
The second draw unit speed	200m/min
		The second orientation oven temperature	25C
The 3rd draw unit speed	200m/min
		The 3rd oven temperature	25C
The 4th draw unit speed	200m/min

According to desired modulus, the distance of fiber stretching 50-500mm in air.3.1 the optimization of different polymkeric substance draft temperatures was at 40: 60 PES: under the situation of PEES multipolymer, the temperature range of experiment is 250 ℃ to 375 ℃.Polymkeric substance shown in the Table I is all estimated in this temperature range, and the melt temperature of select optimizing makes the fiber that can all can obtain best quality from hot melt extruded machine and melt flow indicator.But, for 40: 60 PES of series: the PEES multipolymer, optimize the different of melt temperature and 100%PES, the latter requires minimum melt temperature higher, is 320 ℃.This is in order to reduce melt strength and can to pull out fine-fibered.

Embodiment A 4

PES: the weather resistance of PEES polymkeric substance under the hot melt extrusion condition

Employing has the RDS rheometer of parallel plate and has tested 40: 60 PES that end up with amine: PEES, 9K sample.A polymer samples is heated to 290 ℃,, and constant temperature keeps more than 3 hours.During this period, the rheological property of resin has very little variation.This point by polymkeric substance before heating and afterwards NMR experiment confirmed.NMR demonstrates polymericular weight and the end group number does not change.

Thus, flexible polymer element of the present invention or supporting structure are that carrier just can seasoning reach the several years and not dissolve under room temperature or comparatively high temps, and only when solvent contact, parts just can minute dissolve to a couple of days at approximate number.

Embodiment A 5

The mechanical property of fiber

Tested in this embodiment all fibres fiber modulus, intensity, toughness and elongation % etc. performance.Use the general purpose I nstron trier of model 5544 to carry out these tests.Instron is equipped with 5N tension force/force of compression transmitter.Adopt 100mm gauge length and 50mm/min test speed for each sample.Test is carried out in the controlled experiment room environmental of 23 ℃ of temperature, relative humidity 50%.

For every kind of material, tested a minimum 10-15 sample.

From then on the performance that obtains in the measuring mechanical property is:

1. the rigidity that obtains by tensile modulus;

2. the intensity that obtains by maximum tensile stress (being used for calculating D Tex);

3. by the getable toughness of fracture;

4. displacement or elongation %.

In addition, also observed flexibility.This flexibility is experimental, is inverse ratio with diameter, is the function of modulus.

Following table shows in detail the mechanical property of the multiple thermoplastic fibre of preparation (laboratory extruder) in embodiment 1.

The polymer fiber type	The MW/ end group of polymer fiber	Elongation %	Maximum stress (Mpa)	Energy-to-break/unit surface U/mJ/mm 3	Modulus (Gpa)
						PES∶PEES 40∶60	7K, chlorine are terminal	27	??42	929	????1.44
PES∶PEES 40∶60	15K, chlorine are terminal	48	??171	5764	????3.29
						PES∶PEES 40∶60	9K, amine are terminal	55	??104	4451	????5.01
PES∶PEES 40∶60	12K, amine are terminal	52	??93	3088	????4.81
						PES∶PEES 40∶60	15K, amine are terminal	55	??98	4164	????4.3
PES	24K, the OH end	30	??116	2627	????4.5

Content according to their internal performance, just can be selected flexible member may by polymer type obviously as can be seen from table, so as stitching be provided, weave, the desired performance of comingling, or the function of other desired supporters or carrier.

Should be noted that all fibres in the table all prepares on laboratory extruder, like this, it is proximate that described result just should regard as, and some results can be different with fiber quality.

Embodiment A 6

The comparison following table of non-other fiber types of the present invention shows in detail and PES: the measuring mechanical property result of the fiber that 40: 60 copolymer based fibers of PEES are different.

Polymer fiber	Elongation %	Maximum stress (Mpa)	Energy-to-break/unit surface U/ (mJ/mm 3)	Modulus (Gpa)
					100％PEEK	116	??110	8674	2.07
Polyester (trade(brand)name PES)	33	??24	-	0.2
					Polyester (trade(brand)name TRIVERA)	36	??15	-	0.13

PES and TRIVERA both are the general examples of the multifilament polyester suture of purchase, and they are used for sewing up carbon fibre fabric.Should be noted that the every other fiber of being tested all is the example of one filament fiber.

The supporting structure of B part-contain soluble fiber and dissolving resin matrix is a carrier

Embodiment B 1

The solvability of fiber in Resins, epoxy

This test adopts hot-stage microscope to carry out.One single fiber is placed between two microslides, adds Resins, epoxy.Slide glass is put into hot-stage microscope, material is heated to 180 ℃ with 2 ℃/min speed from room temperature.

Then, measure the solubility property and the record of fiber.

The amine that is dissolved in Araldite PY306 (Ciba Geigy) Resins, epoxy is terminal 40: 60PES: the test result that concerns between the solubility property of PEES 9K and the temperature shows, even being low to moderate under 90-100 ℃ the temperature, polymer dissolution is arranged also.Along with temperature continues to raise, the solvability of polymer fiber also increases.At last,, no longer see fiber, i.e. dissolving fully at 180 ℃.

These observationss are very important, do not dissolve because fiber self is taken under the low injection temperature.If fibrolysis so just can be in injection process, the resin flow forward position, will be taken away the dissolved polymers fiber when resin flow is left the LM mould when exit end flows from one side of injection port.In fact, the solvability of polymer fiber is finished and mold injects/inlet and outlet do not show before the closure in the initial injection/injection of resin.Just after, fiber slowly dissolves when being increased to final solidification value along with the temperature of LM mould.

In this stage, polymer dissolution also enters thermoset solidified step of reaction, finally to being separated and toughness reinforcing LM composite component.

Be dissolved in the MY0510 Resins, epoxy is 40: 60 terminal PES: PEES with amine, concern between 9K solubility property and the temperature, its test result shows once more, can see that polymer fiber is taking place to dissolve in the temperature that is low to moderate 70-80 ℃ in this specific epoxy, and in MY721 Resins, epoxy, under 110-120 ℃ of temperature, dissolve.

Test does not have the identical PES of DDS solidifying agent yet: the PEES system.Do not have difference or difference to ignore to the MY epoxy, but to the PY epoxy, solvent temperature increase.

Figure B1 is by experiment photographic image ground dissolution process.

Figure B1a and B1b have shown the temperatur-timel curve of fibrolysis in Resins, epoxy of different formulations, also shown dissolution time and the gel time under the differing temps, show that the present invention can very carefully control the initial of dissolving and gel, guarantee fiber dissolving fully before the beginning gel.

Embodiment B 2

Dispersion and the measuring mechanical property of soluble fiber in resinous substrates

Figure B2a has shown the measuring mechanical property plate of making.

Figure B2b-B2d has shown Raman's spectrogram of cured composite.Microscope focuses on positions different on the resin board, and only in surface underneath, these positions are at a distance of several nm.

Adopt 800 microns pin holes of Raman, 633nm laser focuses on microscope the different sites (at a distance of several mm) that polishes on the resin board.

The only wave number displacement peak of identification soluble fiber and polysulfone polymer is at 790cm ^-1, this peak has shown important signal/noise ratio, is unlikely covered by the peak of virgin resin matrix.

In analytical results, we have measured 790cm ^-1The relative intensity at band and near peak.Compare with other features, this band keeps very similar intensity.Even 20 different zones, the spectrogram shape also covers finely, this has confirmed that the soluble polymer fibrolysis is also very even in thermoset resin substrate.

Figure B2d has shown 20 different sites 740-880 the spectrogram that the zone is interior, shows that these spectrograms are very accurately synergetic, illustrates that polysulfones is very even in the concentration at each position.

Embodiment B 3

The measuring mechanical property of the virgin resin of soluble fiber and resinous substrates

Test is carried out on several plates made from the different content soluble fiber.

The fracture toughness of representing with energy Gc is identical with the fracture toughness of representing with intensity Kc.

Measuring mechanical property result's standard deviation very low (about 5%) illustrates that the diffusion of thermoplasticity properties-correcting agent after dissolving is fine.(modulus in flexure, tensile yield strength and Tg) is also identical for other performances that record.

Figure B3a and B3b have shown the fracture toughness that energy and intensity are represented respectively, and the result almost is consistent, and under every kind of situation of thermoplastic resin content＜10% and＞17%, the system that contains soluble fiber all shows higher Gc and Kc.

Compress shearing resistance in (CIA), the plane after having tested compression, stretching, impact onboard, institute's value is comparable with the plate that is purchased, and demonstrates good homogeneous, does not have layering.It also is comparable that the tension force G1c of open aperture and G2c estimate.

Embodiment B 4

Morphological research

Contain MDEA that PY306, LonzaChemical that MY0510, Ciba Geigy that Shell Chemicals makes make make and be 40: 60 terminal PES: PEES with amine, the following resin formulation of the staple fiber of 9K mixes, before 170 ℃ of curing 3 hours, in about 90 ℃ of degassings.With the sample polishing of cured plate, corrosion is observed with scanning electronic microscope (SEM).Use 15,22.5 and 30% to cut off the following resin formulation of dimension preparation:

Resin Composition	Formulation A%	Formulation B%	Formulation C%
				MY0510	25.03	22.08	20.6
MY721
				PY306	26.27	23.23	21.7
MDEA	24.82	21.9	20.44
				40: 60 PES of amine end: PEES, the 9K fiber	15	22.5	30

General form is shown in figure B4.

Embodiment B 5

Solubility in other resinous substrates

Polysulfone fibre is dissolved in the L10 cyanate that viscosity and water work as.Therefore injection is easy to.The dissolving power of L10 is than epoxy height, because its viscosity is lower.The consistency of it and polysulfones is also better.

Find fiber 100,110,120,130 and 140 ℃ of dissolvings, dissolution time foreshortened to 3 minutes from 20 minutes.

Then, fibrolysis in the mixture of L10 and epoxy MY0510, is made it to be separated.This resin still can be injected well, and cyanate reduces the viscosity of blend, and epoxy then produces desired being separated.

The supporting structure that C partly contains soluble fiber and binary resinous substrates (thermoset and thermoplastic polymer) is a carrier

Embodiment C 1

The morphological research of cured resin

With a single PES: the PEES fiber dispersion is in 40: 60PES: in the PEES/ Resins, epoxy (content of PES: PEES is about 10-15%), take microphotograph then on hot-stage microscope.After the dissolving, microscopic fields of view is adjusted to sees the body sample.Observe significantly at 175 ℃ after 30 minutes and be separated.

The supporting structure of D part-comprise soluble fiber and structural fibers is a carrier: structure

Embodiment D1

The multidirectional fabric structure

Figure D1 has shown some different use-patterns of multidirectional fiber, and these fibers are entered along the structural fibers combination, and has shown the use as suture.

Embodiment D2

In non-crimps, use soluble fiber as suture

Figure D2 has shown with currently known methods solvable linear slit is gone into to be in the carbon fiber of non-crimps.When being used for curable compositions, the suture dissolving forms the surface of slick non-gauffer.

Embodiment D3

Specific fiber row puts (TFP)

With fiber as upper and lower line, stitching speed 1200 pins/minute, fiber is placed along the structure C fiber, also be placed on around the circle that cuts out and the rectangle etc.Structure is shown in figure D3.

Embodiment D4

The assembling of fabric and prefabrication structure

Figure D4 has shown the prefabrication with several fabrics that assemble.

Embodiment D5

Use the sclerosis of the Woven fabric of soluble fiber

Figure D5 shows a plate, carried out in the plate intersect sewing up, and the harness threading satin of the light weight of hardening 5, purpose is to make it stable when standing to shear in the course of processing.

Embodiment D6

Use the folded seam of soluble fiber suture as prefabrication

D6 shows a plate, has carried out sewing up the usefulness that folds when forming wiring for shaping and assembling in the plate.

Embodiment D7

Hybrid fabric

Figure D7a-7c has shown carbon fiber and PES: the PEES yarn mix Woven fabric.

The supporting structure of E part-comprise soluble fiber and structural fibers and resinous substrates is a carrier

Embodiment E 1

The comparison of fibre property

Figure E1a-c has shown solvable PES in the multidirectional fabric: the contrast of the solubility of PEES suture and polyester suture.Plate adopts with polyester and PES: identical fabric style/weight and alternating layer (one deck polyester suture, one deck PES: PEES suture etc.) make that PEES 60Tex fiber is sewed up.Described plate stands 125 ℃ of high temperature, is retained to and dissolves.

In the drawings, PES: the PEES fibrolysis must not have vestige, but the polyester suture still can be seen.

Embodiment E 2

Fiber is in the deliquescent comparison of differing temps

Figure E2a-E2b is with structure (0,90) row puts the SEM of cross section photographs of 10 layers laminate, shown dissolving, on the two sides of c fiber, each laminate all be along broadwise inweave with Resins, epoxy injection and remain on and solidify the yarn or the polysulfone fibre of after fixing then under the differing temps.Demonstrate incomplete dissolving when remaining on 105 ℃, and when remaining on 135 ℃, vestige is can't see in just dissolving fully of fiber.

The supporting structure of F part-contain soluble fiber and structural fibers and two yuan of resins (thermoset and thermoplasticity) matrix is a carrier.

Embodiment F 1

At supporting structure is the control of fibre weight in the carrier

Continuously, the amount of staple fiber or woven soluble fiber can weigh in advance, and together arranges with desired mode and structural fibers and/or matrix according to the present invention and to put, and the desired amount that comes from the soluble fiber polymkeric substance is provided.

Present embodiment illustrated sew up as mentioned above or the situation of weaving structure fiber under, the fiber of adding guarantees the amount of desired soluble fiber from flexible polymer element as calculated.

Preparation contains the curable compositions of common Woven fabric or polysulfone fibre and structural fibers.Require formed cured composite to comprise 35% resinous substrates and 65% structural carbon fiber, described resinous substrates comprises Resins, epoxy and PES: the PEES resin.These ratios are scattered in the curable compositions, comprise 25% weight resinous substrates and 75 weight % ratios and be 65: the 10 structural carbon fiber and the PES of (corresponding to percentage 100: 16): PEES soluble fiber, described resinous substrates comprise the epoxy and the following PES of 10 weight %: the PEES of same amount.

The structural carbon fiber will be arranged and be set to Tex _Sf(the weight g of the structural carbon fiber of long 1000m)=800.

By formula Tex _Fpe=(weight _Sf% * weight _Fpe%)/Tex _Sf

Tex _fpe＝100×16/800＝2

By these method of calculation, just can set the machine of weaving parameter (fibrous bundle/cm) provide desired calculate Tex _Fpe

Embodiment F 2-is a carrier with curable components dipping supporting structure

In this embodiment, use the polymkeric substance shown in the top Table A I.

Add epoxy or the epoxide of measuring shown in the hotlist FII being no more than under 60 ℃ the temperature.Adopt salt of wormwood as catalyzer, fourth support sulfone is as reaction solvent, make between 1mol DCDPS and 2mol-amino-phenol reacts, and preparation is 40: 60 terminal PES with the primary amine: PEES copolymer 1 2K.Aromatic polymer is dissolved in a small amount of methylene dichloride, adds with the respective amount shown in the table FII then.Resin is heated, and its viscosity just reduces, with solvent 60 ℃ of removals.This resin uses immediately or cools off for future use.

With table each consumption shown in the FII, the fortifying fibre that obtains by the method for the foregoing description with resin impregnation and the net of polysulfone fibre, formation content total composition as described below.

Table FII

Resin
			Part A	Epoxy and solidifying agent	17.5％
Part B1	The polysulfones of predissolve	10.5％
			Reinforce
Part B2	Polysulfone fibre	7％
			Part c	Carbon fiber	65％

For example scheme shown in the F2, use hybrid fabric to strengthen structure, for example Woven fabric or multidirectional fabric.

Embodiment F 3-injects supporting structure in curable components be carrier

Implement to inject with currently known methods, come moistening fully and the dipping hybrid fabric, use above-mentioned calculate the consumption of resinous substrates component.

Embodiment F 4

The cured composite of embodiment F 2

The mixture that will obtain in embodiment F 2 stands high temperature makes fibrolysis, stands high temperature after the dissolving again and is cured.

Figure F4a has shown the dissolving of polysulfone fibre in the above-mentioned system that contains different amount polysulfones (0-30%).When having shown the high-content polysulfones, this photo also can dissolve.The slightly long dissolution time of higher concentration polysulfones only be since viscosity higher due to.

Embodiment F 5

The performance of F4 mixture

Toughness

Use 50% thermoplastic resin will obviously improve performances such as toughness.

The increase of thermoplastic resin content can cause toughness improved performances such as Gc and Kc, and is as shown in the table.

Polysulfones %	Gc(kJ/m)	Kc(MPa·m?1/2)
			30％	1.36	0.61
40％	1.51	0.82
			50％	1.82	0.98

The G part-under different pressures or vacuum sandwich being injected RIFT also solidifies

In common RTM or RFI process, a piece prepreg is piled up with predetermined orientation, form sandwich, this sandwich is put against slick metal sheet row, and covered with the successive layers of porous teflon, emission performance fabric and vacuum bag.The thermal compressor pressurized vessel provides the mould in the pressurized atmosphere and the controlled heat of sandwich.This just makes the inside of die assembling thing produce vacuum, and purpose is to extract volatile matter out, and keeps the pressure difference between inside and the outside.Usually flexible sheet or bag are covered with the uncured stacked thing on the mould.Vacuum is applied on the sandwich, and pressure is applied on the outside surface of bag, and compaction pressure is applied on the sandwich, comes these layers of compacting, with too much resin extruded, the volatile matter bubble that stays is extruded.

The atmosphere of supercharging is about 560kPa-690kPa (85psi-100psi) usually.The entire operation of thermal compressor be subjected to computer-controlled.

VARTM only has mould simultaneously owing to using, and uses the vacuum bagged technology to compress prefabrication, thereby has simplified die RTM.The injection of resin is driven by an atm difference between mold cavity and the resin source, and still, the mould filling time can be oversize, and resin can solidify before all filling up.

RIFT provides a kind of " distribution medium ", and it is to have very low flow resistance porous layer, and the approach that is easy to flow through is provided for injecting resin.Resin flows through the distribution medium that is placed on above the sandwich very soon,, flow thickness then downwards by prefabrication.

Embodiment G1

Adopt the inventive method of decompression or environmental stress

This method of the present invention is made up of following steps: use the hybrid fabric that contains structural fibers (carbon fiber, glass fibre, Kevlar etc.) and polysulfones multifilament, the number of described polysulfones multifilament is 30-160Tex, it comprises the single fiber of diameter 30-80 micron, shown in figure G1a.

The structural fibers for example diameter of carbon fiber is about the 6-7 micron usually, and is therefore thin than above-mentioned polysulfone fibre.This diameter difference has just formed " artificial channel ", helps injection, also helps removing air subsequently in sandwich.

Embodiment G2-sample

Use following fabric to make the composite laminate thing.

Fabric	Sample	Aerial weight (gsm)	Warp fiber	Weft fiber
					????A	????5HS	??370	Carbon HTA 6K	Carbon HTA 6K
????B	????5HS	??370+59	Carbon HTA 6K	Carbon HTA 6K+ soluble fiber

Fabric is cut into various rectangles, is of a size of 6 * 4 inches, adopts the RIFT method then, arranges according to (0,90) 8 modes of arrangement, makes the composite laminate thing.

Figure G2 has shown the RIFT equipment that uses among this embodiment.Yellow fabric is to be used for the flow distribution medium of solvent impregnated resin.The T junctor constitutes entrance and exit, and its shape has formed stable flow front.

Size tissue layer lamination carries out, and is cured in 75-180 ℃ of suitable time of insulation of injection then.

What inject is the resin with following prescription:

	％
		PY306	36.86
MY0510	35.42
		44′DDS	27.72

Be the inject time of measuring: plate A-162s, plate B-118s.

Therefore, shorter inject time to the plate that contains soluble fiber.This explanation fiber has formed and has made the easier passage of resin injection.

The SEM photo of figure G2a and G2b is slave plate A, promptly do not have the plate photographs of solvable polysulfone fibre.Can see big space, see even also can know under the visual inspection.

Figure G2c and G2d are from the plate B photographs made from miscellaneous carbon fiber/polysulfone fibre.Under this this situation,, also can not see the space even plate solidifies under the condition of pressure not having.

This method obviously also has an advantage: promptly can not stay insoluble fiber in final assembly is polyester/nylon etc.

Claims (38)

1. flexible polymer element that is used for curable compositions, described flexible polymer element is solid-state, it is suitable for being in than obviously beginning gel and/or the low temperature of solidified temperature at curable compositions, when a component that it dissolves in curable compositions wherein contacted, partial phase change became liquid state at least.

2. flexible polymer element as claimed in claim 1 is characterized in that it is long at least one direction, it comprises textile materials, for example single or plurality of fibers or long filament, band, film or their mixture or Woven fabric.

3. as each described flexible polymer element in claim 1 and 2, it is characterized in that described phase transformation is,, in the resinous substrates component of curable compositions, carry out by dissolving or under heating helps.

4. as each described flexible polymer element among the claim 1-3, it is characterized in that it also contains the fluid rubber with reactive group; Aggregation is granulated glass sphere, rubber grain and be coated with the granulated glass sphere of rubber for example; Metallic particles is Ti, Al or Fe for example; Filler is for example mica, talcum, vermiculite of tetrafluoroethylene, silicon-dioxide, graphite, boron nitride, clay for example, pigment; Nucleator and stablizer be phosphoric acid salt for example; The material of enhancing solvent resistance is fluorine-containing material for example; Fire retardant is metal oxide FeO and TiO for example ₂With blend or segmented copolymer or the random copolymers crystalline polymer that adds of polyetherketone form for example; Tackiness agent is lower molecular weight thermosetting monomer such as epoxy, acrylic acid derivative, cyanate, ester, BMI-type polymer etc. for example; Tackiness agent is epoxy polymer etc. for example; And/or coating.

5. as each described flexible polymer element among the claim 1-4, it is characterized in that it is fiber or the long filament with diameter d, or film or band with thickness t, described d or t are in the scope that reaches 100 microns, be preferably the 1-80 micron, 30-80 micron for example, 30-65 micron more preferably, elongation at break is 1-75%.

6. as each described flexible polymer element among the claim 1-5, it is characterized in that it is included in its second-order transition temperature or softening temperature or higher temperature rubber-like polymkeric substance, be selected from natural or synthetic rubber and elastomerics, thermoplastic material and their mixture, can miscible or immiscible blend, or contain other polymkeric substance and/or monomeric random or segmented copolymers amorphous or crystal form.

7. as each described flexible polymer element among the claim 1-6, it is characterized in that it comprises is selected from following thermoplastic polymer: derivatived cellulose, polyester, polymeric amide, polyimide, polycarbonate, urethane, polyacrylonitrile, poly-(methyl methacrylate), polystyrene and aromatic polymer, polyaryl ether for example, poly-aryl ketones is polyaryl sulfone especially, also comprise and be selected from following multipolymer: polyesteramide for example, polyamidoimide, polyetherimide, aromatic poly, poly-arylide, poly-(ester) carbonic ether, poly-(methyl methacrylate/butyl acrylate), the blend of polyethersulfone-ether ketone and polymkeric substance.

8. as each described flexible polymer element among the claim 1-7, it is characterized in that it comprises at least a poly aromatic sulfone, described poly aromatic sulfone contains repeating unit that ehter bond connects or the repeating unit that also can contain the thioether keyed jointing, and described unit is selected from:

-(PhAPh) _n-

Perhaps also be selected from:

-(Ph) _a-；

Wherein A=CO or SO ₂, Ph is a phenylene, n=1-2 can be a mark, a=1-4, preferred a=1,2 or 3, and can be mark, when a greater than 1 the time, described phenylene connects by single chemical bond is linear, or by-CO-or-SO ₂-in addition divalent group connects, and perhaps directly condense, or for example dialkylaminobenzoic acid, (mixing) aromatic base or cyclic ketones, acid amides, imide, imines etc. condenses by loop section.

9. flexible polymer element as claimed in claim 8, it is characterized in that it comprises the combination of polyethersulfone and polyether ethersulfone keyed jointing repeating unit, wherein phenylene be between-or right-phenylene, preferably right-phenylene, phenylene connects by the divalent group beyond single chemical bond or the sulfone is linear, or condenses.

10. as each described flexible polymer element in claim 8 and 9, it is characterized in that the unit is in described polyaryl sulfone:

(I)XPhSO ₂PhXPhSO ₂Ph(″PES″)，

(II)X(Ph) _aXPhSO ₂Ph(“PEES”)；

Wherein X is O or S, can be different in different units, I to the ratio of II preferably 10: 90-80: between 20.

11. as each described flexible polymer element among the claim 8-10, the number-average molecular weight Mn that it is characterized in that described aromatic polymer is in the 2000-25000 scope, preferably in the 2000-20000 scope.

12., it is characterized in that described aromatic polymer contains to be selected from following side group or terminated radical: OH, NH as each described flexible polymer element among the claim 8-11 ₂, NHR '-or-SH, wherein R ' is alkyl, epoxy, (methyl) acrylate, cyanate, isocyanic ester, acetylene or the ethylidene that contains up to 8 carbon atoms, as ethene, allyl group or maleimide, acid anhydride, oxazoline with contain the monomer of saturation ratio.

13. method for preparing as each described flexible polymer element among the claim 1-12, it comprises vestige etch or mechanical stretching fluoropolymer resin melt, the phase intermediate processing for example floods, evaporation, solvent cast, by the use of thermal means and wet method, or form parts and polymerization by the monomer whose precursor.

14. method as claimed in claim 13, the parts that it is characterized in that described fibers form are like this preparations: provide polymer melt, continuously extruded, export on the spool with the molten state component shape, stand heating and mechanical stretching process, and cool off.

A 15. supporting structure or carrier that curable compositions is used, it comprises at least a as each described flexible polymer element among the claim 1-12, or also can contain structure unit, fortifying fibre preferably, wherein said at least one flexible polymer element exists with solid phase form, it is suitable for being in than obviously beginning gel and/or the low temperature of solidified temperature in curable components, when resinous substrates component that flexible polymer element dissolves in curable compositions wherein contacted, partial phase change became liquid state at least.

16. supporting structure as claimed in claim 15 or carrier, the monofilament or multifilament fiber, band or the film Individual existence that it is characterized in that example in supporting structure or carrier, or together exist with fortifying fibre, the form of supporting structure or carrier comprises fabric, net, Woven fabric, supatex fabric, looping thing, prefabrication, bare cloth, reticulation, pile fabric, rove, prepreg, mixture or stratifide film or intertexture etc. or their mixture, or that sew up, make, wire or similar type.

17. as each described supporting structure or carrier in claim 15 and 16, it is characterized in that described structural fibers or fortifying fibre are insoluble fibers, be selected from for example fiber of organic or inorganic polymkeric substance, carbon, glass, inorganic oxide, carbide, pottery or metal etc.

18. as each described supporting structure or carrier among the claim 15-17, it is characterized in that described structural fibers arranges in desired mode, the flexible polymer element of fibers form is the suture form, it is suitable for carrying out above-mentioned phase transformation in the mode of disperseing partly or be scattered in the whole curable compositions, is formed up to the seamless suture of small part.

19. supporting structure as claimed in claim 18 or carrier, it is characterized in that it comprises such fabric, structural fibers or construction fabric wherein is random, unidirectional or multidirectional, (being total to) linear or (being total to) plane earth is arranged, and the form of flexible polymer element fiber is the suture of anchoring fiber or fabric or their assembly as requested.

20., it is characterized in that described solvable suture is selected from and be used for the directed special fiber that strengthens usefulness arrange thing (TFP), the suture, sclerosis suture, combination suture, non-crimps (NCF) suture that form along desired fold line and the suture that passes thickness (TTF) etc. as each described supporting structure or carrier among the claim 15-19.

21. method for preparing as each described supporting structure or carrier among the claim 15-20, it comprises provides at least one flexible polymer element, fortifying fibre is provided, and by sew up, knitting, distortion, pin are perverse, woven, woollen yarn knitting, looping, non-woven, comingling, arrangement, twisting, coiling, knotting, one-tenth line etc. combine.

22. method as claimed in claim 21, it is characterized in that described supporting structure or carrier make the web-like fabric in a continuous manner, this fabric is optional to be customized by sewing up and weaving in desired mode, for example intersect and sew up, folded seam, directed enhancing etc. are provided to avoid fabric adding the distortion in man-hour.

23. curable compositions, it comprises as each described flexible polymer element or supporting structure or carrier and curable resin matrix among the claim 1-22, together with the fortifying fibre that maybe can have, catalyzer, solidifying agent, additive filler etc. for example.

24. curable compositions as claimed in claim 23 is characterized in that described resinous substrates is selected from especially di maleimide resin, the formaldehyde condensation resins mixture of formaldehyde phenolic resin, cyanate ester resin, isocyanate resin, resol and two or more resins in them especially of Resins, epoxy, addition polymerization resin.

25. as each described curable compositions in claim 23 and 24, it is characterized in that described flexible polymer element and dissolved matrix select as one " dissolving to ", so that not only dissolve in time that requires and temperature, and have good matrix injection performance, dispersiveness, a form, for example be separated and seamless dispersion, if necessary, can select the combination of different viscosity resin this moment, and every kind of resin all works to above-mentioned various performances.

26., it is characterized in that described flexible polymer element comprises liquid high-viscosity polymer or its precursor as each described curable compositions among the claim 23-25.

27. as each described curable compositions among the claim 23-26, it is characterized in that high-load thermoplastic polymer is wherein arranged, therefore, thermoplastic resin just exists as matrix components with liquid phase with first content, also has at least one flexible polymer element to exist with solid phase form with second content.

28. a method for preparing as each described curable compositions among the claim 23-27, it for example comprises by the dipping that interweaves, injection or modes such as injection, mixing flexible polymer element or supporting structure or carrier is contacted with resinous substrates.

29. method as claimed in claim 28 is characterized in that described injection is in room temperature or is lower than under the high temperature of solvent temperature and carries out, and is suitable in room temperature to 100 ℃, preferably carries out in the scope of room temperature to 75 ℃, makes the viscosity of resin suitable.

30., it is characterized in that described injection is to adopt bag, core and/or mould as claim 28 or 29 described methods, also use flute etc. sometimes, to help flow, be 2-300 minute described inject time, preferred 2-120 minute.

31. one kind is prepared and the solidified method cured compositions or mixture, it comprises provides as each described curable compositions among the claim 23-27, some other component is provided, comprise other fortifying fibres, matrix components, additive etc., stand high temperature and reach one section and be suitable for time that flexible polymer element is undergone phase transition, stand high temperature one segment length again and reach and be suitable for making curable resin matrix generation gel and/or solidified time.

32. method as claimed in claim 31, it is characterized in that it comprises deaeration stage, the described degassing is under room temperature or decompression, each described flexible polymer element or supporting structure or carrier structure among the claim 1-20 are carried out, the fiber of wherein said two kinds of different diameters is arranged with multidirectional arrangement mode altogether, thereby between fiber, form passage, help air flowing.

33. as each described method in claim 31 and 32, it is characterized in that it comprises that standing 100-300 ℃ of high temperature reaches 45 fens clock times, preferred 0.5-35 minute, to realize phase transformation.

34. as each described method in claim 29 and 30, it is characterized in that described gel or the Procuring temperature in 100-175 ℃ of scope carries out, solidify and the temperature of presumable after fixing in 180-400 ℃ of scope carried out for example 1-4 hour.

35. cover parts, the dissolving that it comprises each described flexible polymer element among the claim 1-12, be suitable for dissolving flexible member may is to resinous substrates with as each described supporting structure of claim 15-20 or carrier or as the presumable fortifying fibre of parts in addition, together with any other fortifying fibre, matrix, monomer or polymkeric substance, solidifying agent etc.

36. select or method that blend is suitable for helping to dissolve the resinous substrates of each described flexible polymer element among the claim 1-12 for one kind, this method is carried out according to their classification, molecule type etc.

37. the complex structure body of a shaping, it is made without mould, it comprises some assembled parts, in these assembled parts, use as each described flexible polymer element among the claim 1-12, this flexible polymer element is through weaving or sewing up into, its effect is to produce mechanical property and/or produce the enhancing of planarity, folded seam, hinged joint and bolt hole, directed enhancing etc., for the assembling thing, these each several parts assemble as suture with flexible polymer element, so that during injecting resin that structure is fixing on the throne.

38. as claim 1-12; 15-20; each described flexible polymer element among the 23-27; supporting structure or carrier; prepreg or prefabrication; curable compositions or solidified mixture or resinite; they can be used for the preparation engineering mixture; be used for aviation; automobile; submarine; wind energy; in the industrial use; be used for sports goods and paper mill; as roller; tinsel; the tackiness agent of usefulness such as electronic isolation thing; the usefulness of functional or protective coating; especially use as the serving textile that for example constitutes in the car body parts; as reinforcing membrane monofilm for example; as strengthening or being used for the preparation pipe as the silk thread winding; case; roller, or be used for for example bridge etc. of enhancement engineering structure.

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